2-in-1 sanitizing and rinse aid compositions employing amine based surfactants in machine warewashing

ABSTRACT

Sanitizing cleaning/rinse aid compositions for various applications including institutional machine warewash sanitizing are disclosed. In particular, concentrated and use compositions, such as concentrated liquid rinse aid compositions or ware wash detergents, employing an amine-based surfactant and a defoaming agent are disclosed. In particular, the present disclosure provides compositions and methods for providing a sanitizing rinse with desired antimicrobial efficacy against a broad spectrum of gram-negative microbes, suitable foaming profiles, and beneficial applications of use of the same.

CROSS REFERENCE TO RELATED APPLICATION

This is a Continuation application of U.S. Ser. No. 17/301,039, filedMar. 23, 2021, which claims priority under 35 U.S.C. § 119 toProvisional Application U.S. Ser. No. 62/993,172, filed on Mar. 23,2020, which is herein incorporated by reference in its entiretyincluding without limitation, the specification, claims, and abstract,as well as any figures, tables, or examples thereof.

TECHNICAL FIELD

Embodiments herein relate generally to the field of warewash sanitizingand rinse aids and methods of employing the same. In particular, thesanitizing and rinse aid compositions disclosed herein have excellentantimicrobial activity and may be employed as a 2-in-1 sanitizing rinseaid with surface activity and enzyme compatibility. Methods of employingthe sanitizing and rinse aid compositions are also disclosed.

BACKGROUND

Antimicrobial agents are chemical compositions that are used to preventmicrobiological contamination and deterioration of products, materials,and systems. Antimicrobial agents and compositions are used, forexample, as disinfectants or sanitizers in association with hard surfacecleaning, food preparation, animal feed, cooling water, hospitalityservices, hospital and medical uses, and pulp and paper manufacturing,and cleaning textiles. Of the diverse categories of antimicrobial agentsand compositions, quaternary ammonium compounds represent one of thelargest of the classes of agents in use. At low concentrations,quaternary ammonium type antimicrobial agents are bacteriostatic,fungistatic, algistatic, sporostatic, and tuberculostatic. At mediumconcentrations they are bactericidal, fungicidal, algicidal, andviricidal against lipophilic viruses. It is desirable to boost theantimicrobial activity of such chemicals for us in various applications.

Mechanical warewashing machines including dishwashers have been commonin the institutional and household environments for many years. Suchautomatic warewashing machines clean dishes using two or more cycleswhich can include initially a wash cycle followed by a rinse cycle. Suchautomatic warewashing machines can also utilize other cycles, forexample, a soak cycle, a pre-wash cycle, a scrape cycle, additional washcycles, additional rinse cycles, a sanitizing cycle, and/or a dryingcycle. Any of these cycles can be repeated, if desired and additionalcycles can be used. Rinse aids are conventionally used in warewashingapplications to promote drying and to prevent the formation of spots onthe ware being washed.

In order to reduce the formation of spotting, rinse agents have commonlybeen added to water to form an aqueous rinse that is sprayed on thedishware after cleaning is complete. The precise mechanism through whichrinse agents work is not established. One theory holds that thesurfactant in the rinse agent is absorbed on the surface at temperaturesat or above its cloud point, and thereby reduces the solid-liquidinterfacial energy and contact angle. This leads to the formation of acontinuous sheet which drains evenly from the surface and minimizes theformation of spots. Generally, high foaming surfactants have cloudpoints above the temperature of the rinse water, and, according to thistheory, would not promote sheet formation, thereby resulting in spots.Moreover, high foaming materials are known to interfere with theoperation of warewashing machines.

In addition to detergents and sanitizers, rinse aids are alsoconventionally used in warewashing applications to promote drying and toprevent the formation of spots on the ware being washed. In order toreduce the formation of spotting, rinse aids have commonly been added towater to form an aqueous rinse that is sprayed on the ware aftercleaning is complete. A number of rinse aids are currently known, eachhaving certain advantages and disadvantages, such as those disclosed inU.S. Pat. Nos. 3,592,774, 3,625,901, 3,941,713, 4,005,024, 4,187,121,4,147,559, 4,624,713. In addition, further disclosure of rinse additivesincluding nonionic surfactants is disclosed in Schick, “NonionicSurfactants”, published by Marcel Dekker, and John L. Wilson, Soap andChemical Specialties, February 1958, pp. 48-52 and 170-171, which isherein incorporated by reference in its entirety.

There remains an ongoing need for alternative and improved rinse aidcompositions. There further remains an ongoing need for improvedefficacy of dishmachines, including maximizing the efficacy of thecombination of detergents, sanitizers and/or rinse aids formulations.Current sanitizing rinse aids generally employ chlorine, oxidizers, andquaternary ammonium chloride compounds. These compounds may reduce acomposition's beneficial properties, for example by being corrosive ornot being compatible with enzymes due to their oxidizing ability.

Accordingly, it is a feature of the disclosure to develop concentratedand use liquid compositions as well as solid compositions and methods ofusing the same for warewashing applications to provide desired asanitizing rinse aid employing an amine-based surfactant, which are notknown to be used as sanitizing agents in a machine ware washingapplication.

It is a further feature of the disclosure to provide a sanitizing rinseaid employing an amine surfactant compound effective at low temperaturewarewashing applications.

A further feature of the disclosure is to provide a sanitizing rinse aidthat is free of chlorine, oxidizers, and quaternary ammonium chloride.

Other embodiments, advantages and features of the present disclosurewill become apparent from the following specification taken inconjunction with the accompanying drawings.

SUMMARY

An advantage of the disclosure is the concept that amine-basedsurfactants can perform as a sanitizing agent in ware washingapplications as a part of a cleaning composition or a rinse aid.Beneficially, the sanitizing composition is suitable for use in both lowand high temperature warewashing applications, including institutionalmachine sanitizing. A sanitizing amine surfactant compound based formulais particularly well suited for low temperature and low foamapplications including for example, auto-dish rinse aid and sanitizercombination product, or a 2-in-1 sanitizing rinse.

In some embodiments, compositions and methods of making the same providea sanitizing cleaning/rinse composition containing an amine surfactantwith sanitizing activity. In an aspect, the sanitizing rinse/cleaningcomposition is provided including an amine surfactant having the generalformula:

wherein groups R₁ is a linear or branched, saturated or unsaturatedC₆-C₁₈ alkyl group or H, and R₂ and R₃ are selected from the group of H,(CH₂)₃NH₂, (CH₂)₃NHCH₂COOH, CH₂COOH, (CH₂)₃N(CH₂COOH)₂, (CH₂)₃NH₂. In anaspect, the sanitizing rinse composition is provided as a use solutionpH of 1-13, a pH between about 5 and about 13, or a pH between about 7and about 12, or a pH between about 7 and about 9. In an aspect, thesanitizing rinse composition is substantially free of other sanitizingcompounds, such as chlorine, oxidizers, and quaternary ammonium chlorideand acts as a non-oxidizing sanitizer.

In an embodiment, the present disclosure provides a 2-in-1 sanitizingrinse composition. In a further embodiment, the present disclosureprovides methods of employing the 2-in-1 sanitizing rinse composition.Methods of rinsing a surface or target and providing sanitizingantimicrobial efficacy is provided wherein the method includes applyingto a substrate an amine surfactant composition as disclosed according tothe various embodiments. In an aspect, the combination provides at least5 log kill.

Further embodiments also may include a nonionic surfactant as a foamsuppressant or defoaming agent in combination with the sanitizingsurfactant.

Methods of making the composition are also contemplated.

While multiple embodiments are disclosed, still other embodiments of thepresent disclosure will become apparent to those skilled in the art fromthe following detailed description, which shows and describesillustrative embodiments of the disclosure. Accordingly, the drawingsand detailed description are to be regarded as illustrative in natureand not restrictive.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is a graphical representation of the critical micelle plots ofthe amine surfactant bis(3-aminopropyl) dodecylamine showing a pHdependent response with respect to CMC likely due to, as the pH shiftsfrom alkaline pH 9, to neutral pH 7, and finally pH 5, the amine basedsurfactant is becoming more cationic (protonated) in nature resulting inhigher electrostatic repulsion, and raising the CMC by an order ofmagnitude.

FIG. 2 is a graphical representation of the critical micelle plots ofthe amine surfactant N-alkyl aminopropyl glycine showing a pH dependentresponse with respect to CMC likely due to, as the pH shifts fromalkaline pH 9, to neutral pH 7, and finally pH 5, the amine basedsurfactant is becoming more cationic (protonated) in nature resulting inhigher electrostatic repulsion, and raising the CMC by an order ofmagnitude.

FIG. 3 is a graphical representation of the antimicrobial potency ofbis(3-aminopropyl) dodecylamine at a pH of 5 as expressed by the logreduction of Staphylococcus aureus and E. coli.

FIG. 4 is a graphical representation of the antimicrobial potency ofbis(3-aminopropyl) dodecylamine at a pH of 7 as expressed by the logreduction of Staphylococcus aureus and E. coli.

FIG. 5 is a graphical representation of the antimicrobial potency ofbis(3-aminopropyl) dodecylamine at a pH of 9 as expressed by the logreduction of Staphylococcus aureus and E. coli.

FIG. 6 is a graphical representation of the antimicrobial potency of anamine surfactant mix at a pH of 5 as expressed by the log reduction ofStaphylococcus aureus and E. coli.

FIG. 7 is a graphical representation of the antimicrobial potency of anamine surfactant mix at a pH of 7 as expressed by the log reduction ofStaphylococcus aureus and E. coli.

FIG. 8 is a graphical representation of the antimicrobial potency of anamine surfactant mix at a pH of 9 as expressed by the log reduction ofStaphylococcus aureus and E. coli.

FIG. 9 is a graphical representation showing that the addition of anonionic surfactant does not impact the sanitizing effect ofbis(3-aminopropyl)dodecylamine on Staphylococcus aureus and E. coli.

FIG. 10 is a graphical representation showing the results of a proteinsoil removal test at neutral detergent pH with or without a protease andwith or without an amine surfactant. The lower the rating the moredetergency achieved.

FIG. 11 is a graphical representation showing the results of a proteinsoil removal test at different basic detergent pHs with either aprotease or an endo-peptidase and with an amine surfactant. The lowerthe rating the more detergency achieved.

Various embodiments of the detergent compositions and their methods ofuse will be described in detail with reference to the figures. Referenceto various embodiments does not limit the scope of the disclosures.Figures represented herein are not limitations to the variousembodiments and are presented for exemplary illustration of thedetergent compositions disclosed herein.

DETAILED DESCRIPTION

The embodiments of this disclosure are not limited to particularcompositions, methods of making and/or methods of employing the same forrinsing and other applications, which can vary and are understood byskilled artisans. So that the disclosure may be more readily understood,certain terms are first defined. It is further to be understood that allterminology used herein is for the purpose of describing particularembodiments only and is not intended to be limiting in any manner orscope. For example, as used in this specification and the appendedclaims, the singular forms “a,” “an” and “the” can include pluralreferents unless the content clearly indicates otherwise. Further, allunits, prefixes, and symbols may be denoted in its SI accepted form.

Numeric ranges recited within the specification are inclusive of thenumbers defining the range and include each integer within the definedrange. Throughout this disclosure, various aspects of this disclosureare presented in a range format. It should be understood that thedescription in range format is merely for convenience and brevity andshould not be construed as an inflexible limitation on the scope of thedisclosure. Accordingly, the description of a range should be consideredto have specifically disclosed all the possible sub-ranges, fractions,and individual numerical values within that range. For example,description of a range such as from 1 to 6 should be considered to havespecifically disclosed sub-ranges such as from 1 to 3, from 1 to 4, from1 to 5, from 2 to 4, from 2 to 6, from 3 to 6 etc., as well asindividual numbers within that range, for example, 1, 2, 3, 4, 5, and 6,and decimals and fractions, for example, 1.2, 3.8, 1½, and 4¾. Thisapplies regardless of the breadth of the range.

Definitions

So that the detergent compositions disclosed herein and use thereof maybe more readily understood, certain terms are first defined. Unlessdefined otherwise, all technical and scientific terms used herein havethe same meaning as commonly understood by one of ordinary skill in theart to which embodiments of the disclosure pertain. Many methods andmaterials similar, modified, or equivalent to those described herein canbe used in the practice of the embodiments of the present disclosurewithout undue experimentation, the preferred materials and methods aredescribed herein. In describing and claiming the embodiments of thepresent disclosure, the following terminology will be used in accordancewith the definitions set out below.

The term “about,” as used herein, refers to variation in the numericalquantity that can occur, for example, through typical measuring andliquid handling procedures used for making concentrates or use solutionsin the real world; through inadvertent error in these procedures;through differences in the manufacture, source, or purity of theingredients used to make the compositions or carry out the methods; andthe like. The term “about” also encompasses amounts that differ due todifferent equilibrium conditions for a composition resulting from aparticular initial mixture. Whether or not modified by the term “about”,the claims include equivalents to the quantities.

The term “actives” or “percent actives” or “percent by weight actives”or “actives concentration” are used interchangeably herein and refers tothe concentration of those ingredients involved in cleaning expressed asa percentage minus inert ingredients such as water or salts.

As used herein, the term “cleaning” refers to a method used tofacilitate or aid in soil removal, bleaching, microbial populationreduction, and any combination thereof. As used herein, the term“microorganism” refers to any noncellular or unicellular (includingcolonial) organism. Microorganisms include all prokaryotes.Microorganisms include bacteria (including cyanobacteria), spores,lichens, fungi, protozoa, virinos, viroids, viruses, phages, and somealgae. As used herein, the term “microbe” is synonymous withmicroorganism.

For the purpose of this patent application, successful microbialreduction is achieved when the microbial populations are reduced by atleast about 50%, or by significantly more than is achieved by a washwith water. Larger reductions in microbial population provide greaterlevels of protection.

As used herein, the term “sanitizer” refers to an agent that reduces thenumber of bacterial contaminants to safe levels as judged by publichealth requirements. In an embodiment, sanitizers for use in thisdisclosure will provide at least a 99.999% reduction (5-log orderreduction). These reductions can be evaluated using a procedure set outin Germicidal and Detergent Sanitizing Action of Disinfectants, OfficialMethods of Analysis of the Association of Official Analytical Chemists,paragraph 960.09 and applicable sections, 15th Edition, 1990 (EPAGuideline 91-2). According to this reference a sanitizer should providea 99.999% reduction (5-log order reduction) within 30 seconds at roomtemperature, 25±2° C., against several test organisms. According toembodiments of the disclosure, a sanitizing rinse provides a 99.999%reduction (5-log order reduction) of the desired organisms (includingbacterial contaminants) at a use temperature. Differentiation ofantimicrobial “-cidal” or “-static” activity, the definitions whichdescribe the degree of efficacy, and the official laboratory protocolsfor measuring this efficacy are considerations for understanding therelevance of antimicrobial agents and compositions. Antimicrobialcompositions can affect two kinds of microbial cell damage. The first isa lethal, irreversible action resulting in complete microbial celldestruction or incapacitation. The second type of cell damage isreversible, such that if the organism is rendered free of the agent, itcan again multiply. The former is termed microbiocidal and the later,microbiostatic. A sanitizer and a disinfectant are, by definition,agents which provide antimicrobial or microbiocidal activity. Incontrast, a preservative is generally described as an inhibitor ormicrobiostatic composition.

As used herein, the term “substantially free”, “free”, “free from”,“substantially free of”, or “free of” refers to compositions completelylacking the component or having such a small amount of the componentthat the component does not affect the performance of the composition.The component may be present as an impurity or as a contaminant andshall be less than 0.5 wt-%. In another embodiment, the amount of thecomponent is less than 0.1 wt-% and in yet another embodiment, theamount of component is less than 0.01 wt-%, less than 0.001% wt-%, lessthan 0.0001% wt-%, or less than 0.00001 wt-%.

As used herein, the term “alkyl” or “alkyl groups” refers to saturatedhydrocarbons having one or more carbon atoms, including straight-chainalkyl groups (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl,octyl, nonyl, decyl, etc.), cyclic alkyl groups (or “cycloalkyl” or“alicyclic” or “carbocyclic” groups) (e.g., cyclopropyl, cyclopentyl,cyclohexyl, cycloheptyl, cyclooctyl, etc.), branched-chain alkyl groups(e.g., isopropyl, tert-butyl, sec-butyl, isobutyl, etc.), andalkyl-substituted alkyl groups (e.g., alkyl-substituted cycloalkylgroups and cycloalkyl-substituted alkyl groups).

Unless otherwise specified, the term “alkyl” includes both“unsubstituted alkyls” and “substituted alkyls.” As used herein, theterm “substituted alkyls” refers to alkyl groups having substituentsreplacing one or more hydrogens on one or more carbons of thehydrocarbon backbone. Such substituents may include, for example,alkenyl, alkynyl, halogeno, hydroxyl, alkylcarbonyloxy, arylcarbonyloxy,alkoxycarbonyloxy, aryloxy, aryloxycarbonyloxy, carboxylate,alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aminocarbonyl,alkylaminocarbonyl, dialkylaminocarbonyl, alkylthiocarbonyl, alkoxyl,phosphate, phosphonato, phosphinato, cyano, amino (including alkylamino, dialkylamino, arylamino, diarylamino, and alkylarylamino),acylamino (including alkylcarbonylamino, arylcarbonylamino, carbamoyland ureido), imino, sulfhydryl, alkylthio, arylthio, thiocarboxylate,sulfates, alkylsulfinyl, sulfonates, sulfamoyl, sulfonamido, nitro,trifluoromethyl, cyano, azido, heterocyclic, alkylaryl, or aromatic(including heteroaromatic) groups.

An “antiredeposition agent” refers to a compound that helps keep soilssuspended in water instead of redepositing onto the object beingcleaned. Antiredeposition agents are useful in the present disclosure toassist in reducing redepositing of the removed soil onto the surfacebeing cleaned.

The term “threshold agent” refers to a compound that inhibitscrystallization of water hardness ions from solution, but that need notform a specific complex with the water hardness ion. Threshold agentssuitable for various cleaning applications include but are not limitedto a polycarboxylic acid polymers, polyacrylate, a polymethacrylate, anolefin/maleic copolymer, and the like.

As used herein, the term “polymer” generally includes, but is notlimited to, homopolymers, copolymers, such as for example, block, graft,random and alternating copolymers, terpolymers, and higher “x” mers,further including their derivatives, combinations, and blends thereof.Furthermore, unless otherwise specifically limited, the term “polymer”shall include all possible isomeric configurations of the molecule,including, but are not limited to isotactic, syndiotactic and randomsymmetries, and combinations thereof. Furthermore, unless otherwisespecifically limited, the term “polymer” shall include all possiblegeometrical configurations of the molecule.

The term “surfactant” as used herein is a compound that contains alipophilic segment and a hydrophilic segment, which when added to wateror solvents, reduces the surface tension of the system.

As used herein, the term “ware” generally refers to items such as eatingand cooking utensils, dishes, and other hard surfaces. Ware also refersto items made of various substrates, including glass, ceramic, china,crystal, metal, plastic or natural substances such as, but not limitedto clay, bamboo, hemp and the like. Types of plastics that can becleaned with the compositions according to the disclosure include butare not limited to, those that include polypropylene (PP), high densitypolyethylene (HDPE), low density polyethylene (LDPE), polyvinyl chloride(PVC), styrene acrylonitrile (SAN), polycarbonate (PC), melamineformaldehyde resins or melamine resin (melamine),acrilonitrile-butadiene-styrene (ABS), and polysulfone (PS). Otherexemplary plastics that can be cleaned using the detergent compositionsdisclosed herein include polyethylene terephthalate (PET) polystyrenepolyamide. As used herein, the term “warewashing” refers to washing,cleaning, or rinsing ware.

As used herein, the term “soil” refers to polar or non-polar organic orinorganic substances including, but not limited to carbohydrates,proteins, fats, oils and the like. These substances may be present intheir organic state or complexed to a metal to form an inorganiccomplex.

As used herein, the term “stain” refers to a polar or non-polarsubstance which may or may not contain particulate matter such as metaloxides, metal hydroxides, metal oxide-hydroxides, clays, sand, dust,natural matter, carbon black, graphite and the like.

The term “weight percent,” “wt-%,” “percent by weight,” “% by weight,”and variations thereof, as used herein, refer to the concentration of asubstance as the weight of that substance divided by the total weight ofthe composition and multiplied by 100. It is understood that, as usedhere, “percent,” “%,” and the like are intended to be synonymous with“weight percent,” “wt-%,” etc.

The methods and compositions of the present disclosure may comprise,consist essentially of, or consist of the components and ingredients ofthe present disclosure as well as other ingredients described herein. Asused herein, “consisting essentially of” means that the methods andcompositions may include additional steps, components or ingredients,but only if the additional steps, components or ingredients do notmaterially alter the basic and novel characteristics of the claimedmethods and compositions.

Sanitizing Cleaning or 2-In-1 Sanitizing Rinse Compositions

The present disclosure relates to dish washing compositions and/or rinseaid compositions with at least one sanitizing amine surfactant and mayalso include a nonionic surfactant. Exemplary ranges of the rinsecompositions are shown in Tables 1A-1C in weight percentage of thedetergent compositions.

TABLE 1A Concentrate liquid compositions. First Second Third ExemplaryExemplary Exemplary Material Range wt-% Range wt-% Range wt-% Aminesurfactant 0.001-95   0.01-75   0.01-50   Defoaming surfactant0.001-50   0.01-35   0.01-25   Additional functional  0-80  0-35  0-15ingredients

TABLE 1B Concentrated liquid compositions with an alcohol alkoxylateand/or an optional builder and/or enzyme. First Second Third ExemplaryExemplary Exemplary Material Range wt-% Range wt-% Range wt-% Aminesurfactant 0.001-95   0.01-75   0.1-50  Defoaming surfactant 0.001-50  0.01-35   0.5-25  Alcohol Alkoxylate 0.001-50   0.01-35   0.1-25 Builder  0-90  0-50  0-15 Enzyme  0-30  0-20  0-15 Additional functional 0-80  0-35  0-15 ingredients Water to 100 to 100 to 100

TABLE 1C Concentrated solid compositions with optional builders and/orenzymes. First Second Third Exemplary Exemplary Exemplary Material Rangewt-% Range wt-% Range wt-% Amine surfactant 0.001-95   0.01-75  0.01-50   Defoaming surfactant 0.001-50   0.01-35   0.01-25  Solidifying agents  1-90  5-80 10-80 Builder  0-30  0-20  0-15 Enzyme 0-30  0-20  0-15 Additional functional  0-80  0-35  0-15 ingredients

The sanitizing cleaning or rinse aid compositions may includeconcentrate solids and/or liquid compositions or may be diluted to formuse compositions, as well as ready-to-use compositions. In general, aconcentrate refers to a composition that is intended to be diluted withwater to provide a use solution that contacts an object to provide thedesired cleaning, rinsing, or the like. The cleaning/rinse aidcomposition that contacts the articles or wares to be washed can bereferred to as a concentrate or a use composition (or use solution)dependent upon the formulation employed in methods. It should beunderstood that the concentration of the sanitizing amine surfactant andother components will vary depending on whether the cleaning compositionis provided as a concentrate or as a use solution.

A use solution may be prepared from the concentrate by diluting theconcentrate with a solvent, such as water, at a dilution ratio thatprovides a use solution having the desired detersive properties. Thewater that is used to dilute the concentrate to form the use compositioncan be referred to as water of dilution or a diluent and can vary fromone location to another. The typical dilution factor is betweenapproximately 1 and approximately 10,000 but will depend on factorsincluding water hardness, the amount of soil to be removed and the like.In an embodiment, the concentrate is diluted at a ratio of between about1:10 and about 1:10,000 concentrate to water. Particularly, theconcentrate is diluted at a ratio of between about 1:100 and about1:5,000 concentrate to water. More particularly, the concentrate isdiluted at a ratio of between about 1:250 and about 1:2,000 concentrateto water. In some embodiments the composition is used in itsconcentrated form.

In an aspect, a use solution of the cleaning composition has betweenabout 1 ppm to about 5000 ppm amine surfactant and between about 1 ppmto about 5000 ppm defoamer. In a preferred aspect, a use solution of thecleaning composition has between about 10 ppm to about 2000 ppm aminesurfactant and between about 1 ppm to about 2000 ppm defoamer. In apreferred aspect, a use solution of the cleaning composition has betweenabout 15 ppm to about 1500 ppm anime surfactant and between about 1 ppmto about 1000 ppm pH defoamer. In a preferred embodiment, the usesolution has about 25 ppm or more of an amine surfactant at a pH higherthan about 5. In addition, without being limited according to thedisclosure, all ranges recited are inclusive of the numbers defining therange and include each integer within the defined range.

The antimicrobial cleaning/rinse aid compositions disclosed herein maybe solid concentrate compositions. A “solid” composition refers to acomposition in the form of a solid such as a powder, a particle,agglomerate, a flake, a granule, a pellet, a tablet, a lozenge, a puck,a briquette, a brick, a solid block, a unit dose, or another solid formknown to those of skill in the art. The term “solid” refers to the stateof the cleaning/rinse aid composition under the expected conditions ofstorage and use of the solid cleaning/rinse aid composition. In general,it is expected that the cleaning/rinse aid composition will remain insolid form when exposed to elevated temperatures of 100° F., 112° F.,and preferably 120° F. A cast, pressed, or extruded “solid” may take anyform including a block. When referring to a cast, pressed, or extrudedsolid it is meant that the hardened composition will not flowperceptibly and will substantially retain its shape under moderatestress, pressure, or mere gravity. For example, the shape of a mold whenremoved from the mold, the shape of an article as formed upon extrusionfrom an extruder, and the like. The degree of hardness of the solid castcomposition can range from that of a fused solid block, which isrelatively dense and hard similar to concrete, to a consistencycharacterized as being malleable and sponge-like, similar to caulkingmaterial.

The cleaning/rinse aid compositions disclosed herein can be madeavailable as concentrates that are diluted (or as multiple concentratesthat are diluted and combined) prior to or at the point of use toprovide a use solution for applications on a variety of surfaces, namelyhard surfaces. An advantage of providing concentrates that are latercombined or diluted is that shipping and storage costs can be reducedbecause it can be less expensive to ship and store a concentrate ratherthan a use solution and is also more sustainable because less packagingis used.

The phrases “cleaning/rinse aid composition” and “sanitizingcleaning/rinse aid composition” refer to the cleaning/rinse aidcomposition provided as a concentrate or as a use composition accordingto the disclosure, which may be provided in a variety of formulations,including for example liquid, solid, powder, paste or gel. The term“concentrate” refers to a relatively concentrated form of thecleaning/rinse aid composition that can be diluted with a diluent toform a use composition. An exemplary diluent that can be used to dilutethe concentrate to form the use composition is water. In general, theuse composition refers to the composition that contacts an article toprovide a desired action. For example, a warewashing cleaning/rinse aidcomposition that is provided as a use composition can contact ware forcleaning the ware. In addition, the concentrate or the dilutedconcentrate can be provided as the use composition. For example, theconcentrate can be referred to as the use composition when it is appliedto an article without dilution. In many situations, it is expected thatthe concentrate will be diluted to provide a use composition that isthen applied to an article.

Amine Surfactant

The 2-in-1 sanitizing rinse compositions according to the disclosureinclude at least one sanitizing amine compound. Certain amines are knownto have antimicrobial activity.

Accordingly, various amine-based compounds with antimicrobial activitymay be used in the compositions of the disclosure. The term “aminebased” generally refers to any compound with the formula:

wherein group R₁ is a linear or branched, saturated or unsaturatedC₄-C₂₄ alkyl group or H. R₂ and R₃ may be the same or different and maybe, but not limited to, H, (CH₂)₃NH₂, (CH₂)₃NHCH₂COOH, CH₂COOH, and/or(CH₂)₃N(CH₂COOH)₂. In some embodiments, R₁ is a saturated carbon chainwith less than 24 alkyl groups. In other embodiments, R₁ is a C₄-C₁₈alkyl group, a C₆-C₁₈ alkyl group, a C₆-C₁₄ alkyl group, and/or mixturesthereof.

The use of these amine based surfactants results in efficiency andprovides excellent antimicrobe efficacy (see FIGS. 3-9 ), rinse aidfunctionality, low CMC (see FIGS. 1 and 2 ), they are non-corrosive,have a low odor, and may be compatible with enzymes (see FIGS. 10-11 ).

In preferred embodiments, the amine-based surfactants includeN-alkylaminopropyl glycerin, bis(3-aminopropyl) dodecylamine,N—C₁₀₋₁₆-alkyltrimethylenediamine reaction products with chloroaceticacid, and/or combinations thereof. By way of example, such asN—C₁₀₋₁₆-alkyltrimethylenediamines reaction products with chloroaceticacid may be represented by the following structures:

where R is linear or branched, saturated or unsaturated C₄-C₂₄ alkylgroup or H.

In other embodiments, the compositions of the disclosure are free ofother antimicrobials, such as chlorine, oxidizers, and quaternaryammonium chloride.

An effective amount of the amine-based surfactant is provided incombination with one or more defoaming agents to provide sanitizingefficacy against a broad spectrum of microbes, including gram negativemicrobes such as E. coli in low temperature dish machines. Suitableconcentrations of the amine based surfactant in a use solution includebetween 1 ppm and about 10,000 ppm, 1 ppm and about 1,000 ppm, 5 ppm andabout 400 ppm, 10 ppm and about 400 ppm, 20 ppm and about 400 ppm, 25ppm and about 400 ppm, 50 ppm and about 400 ppm, 75 ppm and about 400ppm, or 100 ppm and about 400 ppm. Without being limited according tothe disclosure, all ranges recited are inclusive of the numbers definingthe range and include each integer within the defined range.

Defoaming Agents

In embodiments of the disclosure, the compositions disclosed herein mayinclude a defoaming agent. In an embodiment, the compositions disclosedherein include a defoaming agent. In a preferred embodiment, thedefoaming agent is a nonionic surfactant. In a preferred embodiment, thedefoaming agent is a nonionic alkoxylated surfactant. In anotherpreferred embodiment, the defoaming agent is a nonionic surfactanthaving a formula RO—(PO)₀₋₅(EO)₁₋₃₀ (PO)₁₋₃₀, or RO—(PO)₁₋₃₀(EO)₁₋₃₀(PO)₁₋₃₀, wherein R is a C₈₋₁₈ linear or branched alkyl group;EO=ethylene oxide; PO=propylene oxide. Exemplary suitable alkoxylatedsurfactants include ethylene oxide/propylene block copolymers (EO/POcopolymers); poloxamers; alkoxylated, predominantly unbranched fattyalcohols with higher alkene oxides alongside ethylene oxide; cappedEO/PO copolymers; partially capped EO/PO copolymers; fully capped EO/POcopolymers; alcohol alkoxylates; capped alcohol alkoxylates; mixturesthereof, or the like.

Other defoaming agents can include silicone compounds such as silicadispersed in polydimethylsiloxane, polydimethylsiloxane, andfunctionalized polydimethylsiloxane, dimethicone, fatty amides,hydrocarbon waxes, fatty acids, fatty esters, fatty alcohols, fatty acidsoaps, ethoxylates, mineral oils, polyethylene glycol esters, alkylphosphate esters such as monostearyl phosphate, and the like. Adiscussion of defoaming agents may be found, for example, in U.S. Pat.No. 3,048,548 to Martin et al., U.S. Pat. No. 3,334,147 to Brunelle etal., and U.S. Pat. No. 3,442,242 to Rue et al., the disclosures of whichare incorporated by reference herein for all purposes.

Nonionic surfactants generally characterized by the presence of anorganic hydrophobic group and an organic hydrophilic group and aretypically produced by the condensation of an organic aliphatic, alkylaromatic or polyoxyalkylene hydrophobic compound with a hydrophilicalkaline oxide moiety which in common practice is ethylene oxide or apolyhydration product thereof, polyethylene glycol. Practically anyhydrophobic compound having a hydroxyl, carboxyl, amino, or amido groupwith a reactive hydrogen atom can be condensed with ethylene oxide, orits polyhydration adducts, or its mixtures with alkoxylenes such aspropylene oxide to form a nonionic surface-active agent. The length ofthe hydrophilic polyoxyalkylene moiety which is condensed with anyparticular hydrophobic compound can be readily adjusted to yield a waterdispersible or water-soluble compound having the desired degree ofbalance between hydrophilic and hydrophobic properties. According to thedisclosure, the nonionic surfactant useful in the composition is alow-foaming nonionic surfactant. Examples of nonionic low foamingsurfactants useful in the present disclosure include:

-   -   1. Block polyoxypropylene-polyoxyethylene polymeric compounds        based upon propylene glycol, ethylene glycol, glycerol,        trimethylolpropane, and ethylenediamine as the initiator        reactive hydrogen compound. Examples of polymeric compounds made        from a sequential propoxylation and ethoxylation of initiator        are poloxamers and Ethoxylated and propoxylated ethylene        diamines. Poloxamers compounds are difunctional (two reactive        hydrogens) compounds formed by condensing ethylene oxide with a        hydrophobic base formed by the addition of propylene oxide to        the two hydroxyl groups of propylene glycol. This hydrophobic        portion of the molecule weighs from 1,000 to 4,000. Ethylene        oxide is then added to sandwich this hydrophobe between        hydrophilic groups, controlled by length to constitute from        about 10% by weight to about 80% by weight of the final        molecule. Ethoxylated and propoxylated ethylene diamines        compounds are tetra-functional block copolymers derived from the        sequential addition of propylene oxide and ethylene oxide to        ethylenediamine. The molecular weight of the propylene oxide        hydrotype ranges from 500 to 7,000; and, the hydrophile,        ethylene oxide, is added to constitute from 10% by weight to 80%        by weight of the molecule.    -   2. Condensation products of one mole of alkyl phenol wherein the        alkyl chain, of straight chain or branched chain configuration,        or of single or dual alkyl constituent, contains from 8 to 18        carbon atoms with from 3 to 50 moles of ethylene oxide. The        alkyl group can, for example, be represented by diisobutylene,        di-amyl, polymerized propylene, iso-octyl, nonyl, and di-nonyl.        These surfactants can be polyethylene, polypropylene, and        polybutylene oxide condensates of alkyl phenols. Examples        include branched polyoxyethylene nonylphenylether and alkyl        phenol ethoxylate.    -   3. Condensation products of one mole of a saturated or        unsaturated, straight or branched chain alcohol having from 6 to        24 carbon atoms with from 3 to 50 moles of ethylene oxide. The        alcohol moiety can consist of mixtures of alcohols in the above        delineated carbon range or it can consist of an alcohol having a        specific number of carbon atoms within this range.    -   4. Condensation products of one mole of saturated or        unsaturated, straight or branched chain carboxylic acid having        from 8 to 18 carbon atoms with from 6 to 50 moles of ethylene        oxide. The acid moiety can consist of mixtures of acids in the        above defined carbon atoms range or it can consist of an acid        having a specific number of carbon atoms within the range.        Examples include 2-hydroxyethyl dodecanoate, PEG 100 stearate,        and PEG-150 disterate.    -   5. Compounds with the following structure: RO—(PO)₀₋₅(EO)₁₋₃₀        (PO)₁₋₃₀, wherein R is a C8-18 linear or branched alkyl group;        EO=ethylene oxide; PO=propylene oxide.    -   6. Compounds from (1) which are modified, essentially reversed,        by adding ethylene oxide to ethylene glycol to provide a        hydrophile of designated molecular weight; and, then adding        propylene oxide to obtain hydrophobic blocks on the outside        (ends) of the molecule. The hydrophobic portion of the molecule        weighs from 1,000 to 3,100 with the central hydrophile including        10% by weight to 80% by weight of the final molecule.    -   7. Alkoxylated diamines produced by the sequential addition of        propylene oxide and ethylene oxide to ethylenediamine. The        hydrophobic portion of the molecule weighs from 250 to 6,700        with the central hydrophile including 0.1% by weight to 50% by        weight of the final molecule.    -   8. Alkoxylated diamines produced by the sequential addition of        ethylene oxide and propylene oxide to ethylenediamine. The        hydrophobic portion of the molecule weighs from 250 to 6,700        with the central hydrophile including 0.1% by weight to 50% by        weight of the final molecule.    -   9. Compounds from groups (1), (2), (3) and (4) which are        modified by “capping” or “end blocking” the terminal hydroxy        group or groups (of multi-functional moieties) to reduce foaming        by reaction with a small hydrophobic molecule such as propylene        oxide, butylene oxide, benzyl chloride; and short chain fatty        acids, alcohols or alkyl halides containing from 1 to 5 carbon        atoms; and mixtures thereof. Also included are reactants such as        thionyl chloride which convert terminal hydroxy groups to a        chloride group. Such modifications to the terminal hydroxy group        may lead to all-block, block-heteric, heteric-block or        all-heteric nonionics.    -   10. Polyoxyalkylene surface-active agents which are        advantageously used in the compositions of this disclosure        correspond to the formula: P[(C₃H₆)_(n)(C₂H₄O)_(m)H]_(x) wherein        P is the residue of an organic compound having from 8 to 18        carbon atoms and containing x reactive hydrogen atoms in which x        has a value of 1 or 2, n has a value such that the molecular        weight of the polyoxyethylene portion is at least 44 and m has a        value such that the oxypropylene content of the molecule is from        10% to 90% by weight. In either case the oxypropylene chains may        contain optionally, but advantageously, small amounts of        ethylene oxide and the oxyethylene chains may contain also        optionally, but advantageously, small amounts of propylene        oxide.    -   11. Alkoxylated amines or, most particularly, alcohol        alkoxylated/aminated/alkoxylated surfactants. These non-ionic        surfactants may be at least in part represented by the general        formulae:

R²⁰—(PO)_(s)N—(EO)_(t)H,

R₂0-(PO)_(s)N—(EO)_(t)H(EO)_(t)H, and

R²⁰—N(EO)_(t)H;

in which R²⁰ is an alkyl, alkenyl or other aliphatic group, or analkyl-aryl group of from 8 to 20, preferably 12 to 14 carbon atoms, EOis oxyethylene, PO is oxypropylene, s is 1 to 20, preferably 2-5, t is1-10, preferably 2-5, and u is 1-10, preferably 2-5. Other variations onthe scope of these compounds may be represented by the alternativeformula:

R²⁰—(PO)_(v)—N[(EO)_(w)H][(EO)_(z)H]

in which R²⁰ is as defined above, v is 1 to 20 (e.g., 1, 2, 3, or 4(preferably 2)), and w and z are independently 1-10, preferably 2-5.

In an embodiment, the claimed compositions include from about 0.001 wt %to about 50 wt %, from about 0.01 wt % to about 35 wt %, from about 0.01wt % to about 25 wt %, or from about 0.5 wt % to about 25 wt % of one ormore defoaming surfactants. In addition, without being limited accordingto the detergent compositions disclosed herein, all ranges recited areinclusive of the numbers defining the range and include each integerwithin the defined range.

Additional Optional Ingredients

The components of the compositions can further be combined with variousfunctional components. In some embodiments, the compositions includingthe amine surfactants and defoaming agents make up a large amount, oreven substantially all of the total weight of the composition. Forexample, in some embodiments few or no additional functional ingredientsare disposed therein. In other embodiments, additional functionalingredients may be included in the compositions. The functionalingredients provide desired properties and functionalities to thecompositions. For the purpose of this application, the term “functionalingredient” includes a material that when dispersed or dissolved in theaqueous use solution provides a beneficial property in a particular use.

Some particular examples of functional materials are discussed in moredetail below, although the particular materials discussed are given byway of example only, and that a broad variety of other functionalingredients may be used.

In some embodiments, the compositions may include additional functionalingredients including, for example, additional surfactants, includingenzymes, nonionic surfactants, thickeners and/or viscosity modifiers,solvents, solubility modifiers, humectants, metal protecting agents,stabilizing agents, corrosion inhibitors, sequestrants and/or chelatingagents, solidifying agent, sheeting agents, pH modifying components,including alkalinity and/or acidity sources, aesthetic enhancing agents(i.e., colorants, odorants, or perfumes), other cleaning agents,hydrotropes or couplers, buffers, and the like.

In some embodiments, the compositions of the disclosure do not includenonionic surfactants, providing a benefit of a sanitizing rinse aidemploying the amine surfactant and defoaming agent, without theinclusion of a nonionic surfactant for wetting, sheeting and/or rinsingcharacteristics. Instead, the benefit of the disclosure is the surfaceactivity as a result of the biocidal agent employed, namely the aminesurfactant and defoaming agent. Additionally, the compositions can beused in conjunction with one or more conventional cleaning agents, e.g.,an alkaline detergent.

Enzymes

In some embodiments, the compositions of the present disclosure includean enzyme. Preferred enzymes include proteases, amylases, cellulases,lipases, and combinations of the same. More preferred enzymes areproteases. The enzyme is preferably in an amount between about 0 wt. %to about 30 wt. %, from about 0 wt. % to about 20 wt. %, or from about 0wt. % to about 15 wt. %.

Proteases

Any protease or mixture of proteases, from any source, can be used inthe enzymatic detergent compositions, provided that the selected enzymeis stable in the desired pH range (between about 6 and about 9). Forexample, the protease enzymes can be derived from a plant, an animal, ora microorganism such as a yeast, a mold, or a bacterium. Preferredprotease enzymes include, but are not limited to, the enzymes derivedfrom Bacillus subtilis, Bacillus lentus, Bacillus licheniformis andStreptomyces griseus. Protease enzymes derived from B. subtilis are mostpreferred. The protease can be purified or a component of a microbialextract, and either wild type or variant (either chemical orrecombinant). Exemplary proteases include subtilisins, a serineendopeptidase, E.C. 3.4.21.

Amylases

Any amylase or mixture of amylases (E.C. 3.2.1.1), from any source, canbe used in the enzymatic detergent compositions, provided that theselected enzyme is stable in the desired pH range (between about 6 andabout 9). For example, the amylase enzymes can be derived from a plant,an animal, or a microorganism such as a yeast, a mold, or a bacterium.Preferred amylase enzymes include, but are not limited to, those derivedfrom a Bacillus, such as B. licheniformis, B. amyloliquefaciens, B.subtilis, or B. stearothermophilus. Amylase enzymes derived from B.subtilis are most preferred. The amylase can be purified or a componentof a microbial extract, and either wild type or variant (either chemicalor recombinant).

Cellulases

Any cellulase or mixture of cellulases (E.C. 3.2.1.4), from any source,can be used in the enzymatic detergent compositions, provided that theselected enzyme is stable in the desired pH range (between about 6 andabout 9). For example, the cellulase enzymes can be derived from aplant, an animal, or a microorganism such as a fungus or a bacterium.Preferred cellulase enzymes include, but are not limited to, thosederived from Humicola insolens, Humicola strain DSM1800, or a cellulase212-producing fungus belonging to the genus Aeromonas and thoseextracted from the hepatopancreas of a marine mollusk, Dolabellaauricula solander. The cellulase can be purified or a component of amicrobial extract, and either wild type or variant (either chemical orrecombinant).

Lipases

Any lipase or mixture of lipases (E.C. 3.1.1), from any source, can beused in the enzymatic detergent compositions, provided that the selectedenzyme is stable in the desired pH range (between about 6 and about 9).For example, the lipase enzymes can be derived from a plant, an animal,or a microorganism such as a fungus or a bacterium. Preferred proteaseenzymes include, but are not limited to, the enzymes derived from aPseudomonas, such as Pseudomonas stutzeri ATCC 19.154, or from aHumicola, such as Humicola lanuginosa (typically produced recombinantlyin Aspergillus oryzae). The lipase can be purified or a component of amicrobial extract, and either wild type or variant (either chemical orrecombinant).

Other Enzymes

The enzymatic detergent compositions can comprise additional enzymes inaddition to the foregoing. Additional suitable enzymes can include, butare not limited to, cutinases, peroxidases, gluconases, or mixturesthereof.

Alkalinity and/or Acidity Source

In some embodiments, the compositions of the present disclosure includean alkalinity source and/or acidulant. In a preferred embodiment, thecompositions of the present disclosure include an acidulant. Theacidulant can be effective to form a concentrate composition or a usesolution with a desired acidic to neutral pH. The acidulant can beeffective to form a use composition with pH of about 7, about 6 or less,about 5 or less.

In an embodiment, the acidulant includes an inorganic acid. Suitableinorganic acids include, but are not limited to, sulfuric acid, sodiumbisulfate, phosphoric acid, nitric acid, hydrochloric acid. In someembodiments, the acidulant includes an organic acid. Suitable organicacids include, but are not limited to, methane sulfonic acid, ethanesulfonic acid, propane sulfonic acid, butane sulfonic acid, xylenesulfonic acid, benzene sulfonic acid, formic acid, acetic acid, mono,di, or tri-carboxylic acids (succinic, citric), picolinic acid,dipicolinic acid, and mixtures thereof. In some embodiments, thecompositions of the present disclosure are free or substantially free ofa phosphorous based acid. In some embodiments, acidulant selected canalso function as a stabilizing agent. Thus, the compositions of thepresent disclosure can be substantially free of an additionalstabilizing agent.

According to some embodiments, the detergent compositions include analkalinity source. Exemplary alkalinity sources include alkali metalcarbonates and/or alkali metal hydroxides. In various aspects, acombination of both alkali metal carbonates and/or alkali metalhydroxides are employed as the alkalinity source. The alkalinity sourcecan be effective to form a use composition with pH of about 7, about 8or more, about 9 or more, about 9, about 10 or more, about 10, about 11or more, about 12 or more, about 13, or the like.

Alkali metal carbonates used in the formulation of detergents are oftenreferred to as ash-based detergents and most often employ sodiumcarbonate. Additional alkali metal carbonates include, for example,sodium or potassium carbonate. In another embodiments, the alkali metalcarbonates, and alkali metal hydroxides are further understood toinclude bicarbonates and sesquicarbonates. According to the detergentcompositions disclosed herein, any “ash-based” or “alkali metalcarbonate” shall also be understood to include all alkali metalcarbonates, bicarbonates and/or sesquicarbonates.

Alkali metal hydroxides used in the formulation of detergents are oftenreferred to as caustic detergents. Examples of suitable alkali metalhydroxides include sodium hydroxide, potassium hydroxide, and lithiumhydroxide. Exemplary alkali metal salts include sodium carbonate,potassium carbonate, and mixtures thereof. The alkali metal hydroxidesmay be added to the composition in any form known in the art, includingas solid beads, dissolved in an aqueous solution, or a combinationthereof. Alkali metal hydroxides are commercially available as a solidin the form of prilled solids or beads having a mix of particle sizesranging from about 12-100 U.S. mesh, or as an aqueous solution, as forexample, as a 45% and a 50% by weight solution.

In addition to the first alkalinity source, the detergent compositionmay comprise a secondary alkalinity source. Examples of useful secondaryalkaline sources include, but are not limited to, alkali metal silicatessuch as sodium or potassium silicate or metasilicate; alkali metalcarbonates such as sodium or potassium carbonate, bicarbonate,sesquicarbonate; alkali metal borates such as sodium or potassiumborate; and ethanolamines and amines. Such alkalinity agents arecommonly available in either aqueous or powdered form, either of whichis useful in formulating the present detergent compositions.

An effective amount of one or more acidulant and/or alkalinity sourcesis provided in the detergent composition. An effective amount isreferred to herein as an amount that provides a use composition having apH of at least about 5, preferably at least about 7, at least about 9,and at most 13. The use solution pH range is preferably between about 1and about 13, about 5 and about 13, and more preferably between about 7to 9. In addition, without being limited according to the detergentcompositions disclosed herein, all ranges recited are inclusive of thenumbers defining the range and include each integer within the definedrange.

Stabilizing Agents

In some embodiments, the compositions of the present disclosure includeone or more stabilizing agents. In some embodiments, an acidicstabilizing agent can be used. Thus, in some embodiments, thecompositions of the present disclosure can be substantially free of anadditional acidulant. Suitable stabilizing agents include, for example,chelating agents or sequestrants. Suitable sequestrants include, but arenot limited to, organic chelating compounds that sequester metal ions insolution, particularly transition metal ions. Such sequestrants includeorganic amino- or hydroxy-polyphosphonic acid complexing agents (eitherin acid or soluble salt forms), carboxylic acids (e.g., polymericpolycarboxylate), hydroxycarboxylic acids, aminocarboxylic acids, orheterocyclic carboxylic acids, e.g., pyridine-2, 6-dicarboxylic acid(dipicolinic acid).

In other embodiments, the sequestrant can be or include phosphonic acidor phosphonate salt. Suitable phosphonic acids and phosphonate saltsinclude HEDP; ethylenediamine tetrakis methylenephosphonic acid (EDTMP);diethylenetriamine pentakis methylenephosphonic acid (DTPMP);cyclohexane-1,2-tetramethylene phosphonic acid; amino[tri(methylenephosphonic acid)]; (ethylene diamine[tetra methylene-phosphonic acid)];2-phosphene butane-1,2,4-tricarboxylic acid; or salts thereof, such asthe alkali metal salts, ammonium salts, or alkyloyl amine salts, such asmono, di, or tetra-ethanolamine salts; picolinic, dipicolinic acid ormixtures thereof. In some embodiments, organic phosphonates, e.g, HEDPare included in the compositions of the present disclosure. Specificexamples include, but are not limited to, 1-hydroxyethylidene-1,1-diphosphonic acid, amino(tri(methylenephosphonic acid)),(N[CH₂PO₃H2]3), ethylenediamine[tetra(methylenephosphonic acid)], and2-phosphonobutane-1,2,4-tricarboxylic acid.

The sequestrant can be or include aminocarboxylic acid type sequestrant.Suitable aminocarboxylic acid type sequestrants include the acids oralkali metal salts thereof, e.g., amino acetates and salts thereof.Suitable aminocarboxylates include N-hydroxyethylaminodiacetic acid;hydroxyethylenediaminetetraacetic acid, nitrilotriacetic acid (NTA);ethylenediaminetetraacetic acid (EDTA);N-hydroxyethyl-ethylenediaminetriacetic acid (HEDTA);diethylenetriaminepentaacetic acid (DTPA); and Alanine-N, N-diaceticacid; and the like; and mixtures thereof.

The sequestrant can be or include a polycarboxylate. Suitablepolycarboxylates include, for example, polyacrylic acid, maleic/olefincopolymer, acrylic/maleic copolymer, polymethacrylic acid, acrylicacid-methacrylic acid copolymers, hydrolyzed polyacrylamide, hydrolyzedpolymethacrylamide, hydrolyzed polyamide-methacrylamide copolymers,hydrolyzed polyacrylonitrile, hydrolyzed polymethacrylonitrile,hydrolyzed acrylonitrile-methacrylonitrile copolymers, polymaleic acid,polyfumaric acid, copolymers of acrylic and itaconic acid, phosphinopolycarboxylate, acid or salt forms thereof, mixtures thereof, and thelike.

In certain embodiments, the present composition includes about 0 toabout 10 wt-% stabilizing agent, about 0.01 to about 10 wt-% stabilizingagent, about 0.4 to about 4 wt-% stabilizing agent, about 0.6 to about 3wt-% stabilizing agent, about 1 to about 2 wt-% stabilizing agent. It isto be understood that all values and ranges within these values andranges are encompassed by the present disclosure.

Wetting Agents

Also useful in the compositions of the disclosure are wetting agents.Wetting agents function to increase the surface contact or penetrationactivity of the antimicrobial composition of the disclosure. Wettingagents which can be used in the composition of the disclosure includeany of those constituents known within the art to raise the surfaceactivity of the composition of the disclosure. In aspects of thedisclosure various amine surfactants are suitable for the cleaning/rinseaid and sanitizing cleaning/rinse aid application without the use offurther wetting agents in the formulation. Wetting agents can be presentat a concentration range from about 0.01 wt-% to 20 wt-%, 0.01 wt-% to20 wt-%, from about 0.01 wt-% to 5 wt-%, or from about 0.01 wt-% toabout 1 wt-%.

Thickening or Gelling Agents

The compositions of the present disclosure can include any of a varietyof known thickeners. Suitable thickeners include natural gums such asxanthan gum, guar gum, or other gums from plant mucilage; polysaccharidebased thickeners, such as alginates, starches, and cellulosic polymers(e.g., carboxymethyl cellulose); polyacrylates thickeners; andhydrocolloid thickeners, such as pectin. In an embodiment, the thickenerdoes not leave contaminating residue on the surface of an object. Forexample, the thickeners or gelling agents can be compatible with food orother sensitive products in contact areas. Generally, the concentrationof thickener employed in the present compositions or methods will bedictated by the desired viscosity within the final composition. However,as a general guideline, the viscosity of thickener within the presentcomposition ranges from about 0.1 wt-% to about 5 wt-%, from about 0.1wt-% to about 1.0 wt-%, or from about 0.1 wt-% to about 0.5 wt-%.

Additional Surfactants

The sanitizing rinse compositions according to the disclosure mayinclude additional surfactants. In a particular aspect, nonionicsurfactants are particularly useful for applications of use requiringadditional defoaming. In an aspect, it is beneficial the sanitizing andrinse compositions do not require formulation with the nonionicsurfactant for low-foaming surface activity. However, in some aspects, anonionic surfactant may be desired in combination with the compositionsof the disclosure (such as included in a detergent formulation employedin combination therewith). For example, in certain embodiments, such asfood soil defoaming applications, a nonionic surfactant may be desirableto preferably include alcohol alkoxylates and EO/PO block copolymers.

Useful nonionic surfactants are generally characterized by the presenceof an organic hydrophobic group and an organic hydrophilic group and aretypically produced by the condensation of an organic aliphatic, alkylaromatic or polyoxyalkylene hydrophobic compound with a hydrophilicalkaline oxide moiety which in common practice is ethylene oxide or apolyhydration product thereof, polyethylene glycol. Practically anyhydrophobic compound having a hydroxyl, carboxyl, amino, or amido groupwith a reactive hydrogen atom can be condensed with ethylene oxide, orits polyhydration adducts, or its mixtures with alkoxylenes such aspropylene oxide to form a nonionic surface-active agent. The length ofthe hydrophilic polyoxyalkylene moiety which is condensed with anyparticular hydrophobic compound can be readily adjusted to yield a waterdispersible or water-soluble compound having the desired degree ofbalance between hydrophilic and hydrophobic properties. Useful nonionicsurfactants include:

Block polyoxypropylene-polyoxyethylene polymeric compounds based uponpropylene glycol, ethylene glycol, glycerol, trimethylolpropane, andethylenediamine as the initiator reactive hydrogen compound. Examples ofpolymeric compounds made from a sequential propoxylation andethoxylation of initiator are poloxamers and ethoxylated andpropoxylated ethylene diamines. Poloxamers are difunctional (tworeactive hydrogens) compounds formed by condensing ethylene oxide with ahydrophobic base formed by the addition of propylene oxide to the twohydroxyl groups of propylene glycol. This hydrophobic portion of themolecule weighs from about 1,000 to about 4,000. Ethylene oxide is thenadded to sandwich this hydrophobe between hydrophilic groups, controlledby length to constitute from about 10% by weight to about 80% by weightof the final molecule. Ethoxylated and propoxylated ethylene diaminescompounds are tetra-flinctional block copolymers derived from thesequential addition of propylene oxide and ethylene oxide toethylenediamine. The molecular weight of the propylene oxide hydrotyperanges from about 500 to about 7,000; and, the hydrophile, ethyleneoxide, is added to constitute from about 10% by weight to about 80% byweight of the molecule.

Condensation products of one mole of alkyl phenol wherein the alkylchain, of straight chain or branched chain configuration, or of singleor dual alkyl constituent, contains from about 8 to about 18 carbonatoms with from about 3 to about 50 moles of ethylene oxide. The alkylgroup can, for example, be represented by diisobutylene, di-amyl,polymerized propylene, iso-octyl, nonyl, and di-nonyl. These surfactantscan be polyethylene, polypropylene, and polybutylene oxide condensatesof alkyl phenols.

Condensation products of one mole of a saturated or unsaturated,straight or branched chain alcohol having from about 6 to about 24carbon atoms with from about 3 to about 50 moles of ethylene oxide. Thealcohol moiety can consist of mixtures of alcohols in the abovedelineated carbon range or it can consist of an alcohol having aspecific number of carbon atoms within this range.

Condensation products of one mole of saturated or unsaturated, straightor branched chain carboxylic acid having from about 8 to about 18 carbonatoms with from about 6 to about 50 moles of ethylene oxide. The acidmoiety can consist of mixtures of acids in the above defined carbonatoms range or it can consist of an acid having a specific number ofcarbon atoms within the range.

In addition to ethoxylated carboxylic acids, commonly calledpolyethylene glycol esters, other alkanoic acid esters formed byreaction with glycerides, glycerin, and polyhydric (saccharide orsorbitan/sorbitol) alcohols have application in this disclosure forspecialized embodiments, particularly indirect food additiveapplications. All of these ester moieties have one or more reactivehydrogen sites on their molecule which can undergo further acylation orethylene oxide (alkoxide) addition to control the hydrophilicity ofthese substances. Care must be exercised when adding these fatty estersor acylated carbohydrates to compositions of the present disclosurecontaining amylase and/or lipase enzymes because of potentialincompatibility.

Examples of Nonionic Low Foaming Surfactants Include:

Compounds from (1) which are modified, essentially reversed, by addingethylene oxide to ethylene glycol to provide a hydrophile of designatedmolecular weight; and, then adding propylene oxide to obtain hydrophobicblocks on the outside (ends) of the molecule. The hydrophobic portion ofthe molecule weighs from about 1,000 to about 3,100 with the centralhydrophile including 10% by weight to about 80% by weight of the finalmolecule. Likewise, the ethoxylated and propoxylated ethylene diaminesreverse surfactants are produced by the sequential addition of ethyleneoxide and propylene oxide to ethylenediamine. The hydrophobic portion ofthe molecule weighs from about 2,100 to about 6,700 with the centralhydrophile including 10% by weight to 80% by weight of the finalmolecule.

Compounds from groups (1), (2), (3) and (4) which are modified by“capping” or “end blocking” the terminal hydroxy group or groups (ofmulti-functional moieties) to reduce foaming by reaction with a smallhydrophobic molecule such as propylene oxide, butylene oxide, benzylchloride; and, short chain fatty acids, alcohols or alkyl halidescontaining from 1 to about 5 carbon atoms; and mixtures thereof. Alsoincluded are reactants such as thionyl chloride which convert terminalhydroxy groups to a chloride group. Such modifications to the terminalhydroxy group may lead to all-block, block-heteric, heteric-block orall-heteric nonionics.

Additional Examples of Effective Low Foaming Nonionics Include:

The alkylphenoxypolyethoxyalkanols of U.S. Pat. No. 2,903,486 issuedSep. 8, 1959 to Brown et al. and represented by the formula

in which R is an alkyl group of 8 to 9 carbon atoms, A is an alkylenechain of 3 to 4 carbon atoms, n is an integer of 7 to 16, and m is aninteger of 1 to 10.

The polyalkylene glycol condensates of U.S. Pat. No. 3,048,548 issuedAug. 7, 1962 to Martin et al. having alternating hydrophilic oxyethylenechains and hydrophobic oxypropylene chains where the weight of theterminal hydrophobic chains, the weight of the middle hydrophobic unitand the weight of the linking hydrophilic units each represent aboutone-third of the condensate.

The defoaming nonionic surfactants disclosed in U.S. Pat. No. 3,382,178issued May 7, 1968 to Lissant et al. having the general formulaZ[(OR)_(n)OH]_(z) wherein Z is alkoxylatable material, R is a radicalderived from an alkaline oxide which can be ethylene and propylene and nis an integer from, for example, 10 to 2,000 or more and z is an integerdetermined by the number of reactive oxyalkylatable groups.

The conjugated polyoxyalkylene compounds described in U.S. Pat. No.2,677,700, issued May 4, 1954 to Jackson et al. corresponding to theformula Y(C₃H₆O)_(n) (C₂H₄O)_(m)H wherein Y is the residue of organiccompound having from about 1 to 6 carbon atoms and one reactive hydrogenatom, n has an average value of at least about 6.4, as determined byhydroxyl number and m has a value such that the oxyethylene portionconstitutes about 10% to about 90% by weight of the molecule.

The conjugated polyoxyalkylene compounds described in U.S. Pat. No.2,674,619, issued Apr. 6, 1954 to Lundsted et al. having the formulaY[(C₃H₆O_(n) (C₂H₄O)_(m)H]_(x) wherein Y is the residue of an organiccompound having from about 2 to 6 carbon atoms and containing x reactivehydrogen atoms in which x has a value of at least about 2, n has a valuesuch that the molecular weight of the polyoxypropylene hydrophobic baseis at least about 900 and m has value such that the oxyethylene contentof the molecule is from about 10% to about 90% by weight. Compoundsfalling within the scope of the definition for Y include, for example,propylene glycol, glycerine, pentaerythritol, trimethylolpropane,ethylenediamine and the like. The oxypropylene chains optionally, butadvantageously, contain small amounts of ethylene oxide and theoxyethylene chains also optionally, but advantageously, contain smallamounts of propylene oxide.

Additional conjugated polyoxyalkylene surface-active agents which areadvantageously used in the compositions of this disclosure correspond tothe formula: P[(C₃H₆O)_(n) (C₂H₄O)_(m)H]_(x) wherein P is the residue ofan organic compound having from about 8 to 18 carbon atoms andcontaining x reactive hydrogen atoms in which x has a value of 1 or 2, nhas a value such that the molecular weight of the polyoxyethyleneportion is at least about 44 and m has a value such that theoxypropylene content of the molecule is from about 10% to about 90% byweight. In either case the oxypropylene chains may contain optionally,but advantageously, small amounts of ethylene oxide and the oxyethylenechains may contain also optionally, but advantageously, small amounts ofpropylene oxide.

Polyhydroxy fatty acid amide surfactants suitable for use in the presentcompositions include those having the structural formula R₂CON_(R1)Z inwhich: R1 is H, C₁-C₄ hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl,ethoxy, propoxy group, or a mixture thereof; R₂ is a C₅-C₃₁ hydrocarbyl,which can be straight-chain; and Z is a polyhydroxyhydrocarbyl having alinear hydrocarbyl chain with at least 3 hydroxyls directly connected tothe chain, or an alkoxylated derivative (preferably ethoxylated orpropoxylated) thereof. Z can be derived from a reducing sugar in areductive amination reaction, such as a glycityl moiety.

The alkyl ethoxylate condensation products of aliphatic alcohols withfrom about 0 to about 25 moles of ethylene oxide are suitable for use inthe present compositions. The alkyl chain of the aliphatic alcohol caneither be straight or branched, primary or secondary, and generallycontains from 6 to 22 carbon atoms.

The ethoxylated C₆-C₁₈ fatty alcohols and C₆-C₁₈ mixed ethoxylated andpropoxylated fatty alcohols are suitable surfactants for use in thepresent compositions, particularly those that are water soluble.Suitable ethoxylated fatty alcohols include the C₆-C₁₈ ethoxylated fattyalcohols with a degree of ethoxylation of from 3 to 50.

Suitable nonionic alkylpolysaccharide surfactants, particularly for usein the present compositions include those disclosed in U.S. Pat. No.4,565,647, Llenado, issued Jan. 21, 1986. These surfactants include ahydrophobic group containing from about 6 to about 30 carbon atoms and apolysaccharide, e.g., a polyglycoside, hydrophilic group containing fromabout 1.3 to about 10 saccharide units. Any reducing saccharidecontaining 5 or 6 carbon atoms can be used, e.g., glucose, galactose andgalactosyl moieties can be substituted for the glucosyl moieties.(Optionally the hydrophobic group is attached at the 2-, 3-, 4-, etc.positions thus giving a glucose or galactose as opposed to a glucosideor galactoside.) The intersaccharide bonds can be, e.g., between the oneposition of the additional saccharide units and the 2-, 3-, 4-, and/or6-positions on the preceding saccharide units.

Fatty acid amide surfactants suitable for use the present compositionsinclude those having the formula: R₆CON(R₇)₂ in which R₆ is an alkylgroup containing from 7 to 21 carbon atoms and each R₇ is independentlyhydrogen, C₁-C₄ alkyl, C₁-C₄ hydroxyalkyl, or —(C₂H₄O)_(X)H, where x isin the range of from 1 to 3.

A useful class of non-ionic surfactants include the class defined asalkoxylated amines or, most particularly, alcoholalkoxylated/aminated/alkoxylated surfactants. These non-ionicsurfactants may be at least in part represented by the general formulae:R²⁰—(PO)_(S)N—(EO)_(t)H, R²⁰—(PO)_(S)N—(EO)_(t)H(EO)_(t)H, andR²⁰—N(EO)_(t)H; in which R²⁰ is an alkyl, alkenyl or other aliphaticgroup, or an alkyl-aryl group of from 8 to 20, preferably 12 to 14carbon atoms, EO is oxyethylene, PO is oxypropylene, s is 1 to 20,preferably 2-5, t is 1-10, preferably 2-5, and u is 1-10, preferably2-5. Other variations on the scope of these compounds may be representedby the alternative formula: R²⁰—(PO)_(V)—N[(EO)_(w)H][(EO)_(z)H] inwhich R²⁰ is as defined above, v is 1 to 20 (e.g., 1, 2, 3, or 4(preferably 2)), and w and z are independently 1-10, preferably 2-5.Preferred nonionic surfactants for the compositions of the disclosureinclude alcohol alkoxylates, EO/PO block copolymers, alkylphenolalkoxylates, and the like.

The treatise Nonionic Surfactants, edited by Schick, M. J., Vol. 1 ofthe Surfactant Science Series, Marcel Dekker, Inc., New York, 1983 is anexcellent reference on the wide variety of nonionic compounds generallyemployed in the practice of the present disclosure. A typical listing ofnonionic classes, and species of these surfactants, is given in U.S.Pat. No. 3,929,678 issued to Laughlin and Heuring on Dec. 30, 1975.Further examples are given in “Surface Active Agents and detergents”(Vol. I and II by Schwartz, Perry and Berch).

Semi-Polar Nonionic Surfactants

The semi-polar type of nonionic surface-active agents are another classof nonionic surfactant useful in compositions of the present disclosure.Generally, semi-polar nonionics are high foamers and foam stabilizers,which can limit their application in CIP systems. However, withincompositional embodiments of this disclosure designed for high foamcleaning methodology, semi-polar nonionics would have immediate utility.The semi-polar nonionic surfactants include the amine oxides, phosphineoxides, sulfoxides and their alkoxylated derivatives.

Amine oxides are tertiary amine oxides corresponding to the generalformula:

wherein the arrow is a conventional representation of a semi-polar bond;and, R¹, R², and R³ may be aliphatic, aromatic, heterocyclic, alicyclic,or combinations thereof. Generally, for amine oxides of detergentinterest, R¹ is an alkyl radical of from about 8 to about 24 carbonatoms; R² and R³ are alkyl or hydroxyalkyl of 1-3 carbon atoms or amixture thereof; R² and R³ can be attached to each other, e.g. throughan oxygen or nitrogen atom, to form a ring structure; R⁴ is an alkalineor a hydroxyalkylene group containing 2 to 3 carbon atoms; and n rangesfrom 0 to about 20.

Useful water soluble amine oxide surfactants are selected from thecoconut or tallow alkyl di-(lower alkyl) amine oxides, specific examplesof which are dodecyldimethylamine oxide, tridecyldimethylamine oxide,etradecyldimethylamine oxide, pentadecyldimethylamine oxide,hexadecyldimethylamine oxide, heptadecyldimethylamine oxide,octadecyldimethylaine oxide, dodecyldipropylamine oxide,tetradecyldipropylamine oxide, hexadecyldipropylamine oxide,tetradecyldibutylamine oxide, octadecyldibutylamine oxide,bis(2-hydroxyethyl)dodecylamine oxide,bis(2-hydroxyethyl)-3-dodecoxy-1-hydroxypropylamine oxide,dimethyl-(2-hydroxydodecyl)amine oxide, 3,6,9-trioctadecyldimethylamineoxide and 3-dodecoxy-2-hydroxypropyldi-(2-hydroxyethyl)amine oxide.

Useful semi-polar nonionic surfactants also include the water-solublephosphine oxides having the following structure:

wherein the arrow is a conventional representation of a semi-polar bond;and, R¹ is an alkyl, alkenyl or hydroxyalkyl moiety ranging from 10 toabout 24 carbon atoms in chain length; and, R² and R³ are each alkylmoieties separately selected from alkyl or hydroxyalkyl groupscontaining 1 to 3 carbon atoms.

Examples of useful phosphine oxides include dimethyldecylphosphineoxide, dimethyltetradecylphosphine oxide, methylethyltetradecylphosphoneoxide, dimethylhexadecylphosphine oxide,diethyl-2-hydroxyoctyldecylphosphine oxide,bis(2-hydroxyethyl)dodecylphosphine oxide, andbis(hydroxymethyl)tetradecylphosphine oxide.

Semi-polar nonionic surfactants useful herein also include thewater-soluble sulfoxide compounds which have the structure:

wherein the arrow is a conventional representation of a semi-polar bond;and, R¹ is an alkyl or hydroxyalkyl moiety of about 8 to about 28 carbonatoms, from 0 to about 5 ether linkages and from 0 to about 2 hydroxylsubstituents; and R² is an alkyl moiety consisting of alkyl andhydroxyalkyl groups having 1 to 3 carbon atoms.

Useful examples of these sulfoxides include dodecyl methyl sulfoxide;3-hydroxy tridecyl methyl sulfoxide; 3-methoxy tridecyl methylsulfoxide; and 3-hydroxy-4-dodecoxybutyl methyl sulfoxide.

Semi-polar nonionic surfactants for the compositions of the disclosureinclude dimethyl amine oxides, such as lauryl dimethyl amine oxide,myristyl dimethyl amine oxide, cetyl dimethyl amine oxide, combinationsthereof, and the like. Useful water soluble amine oxide surfactants areselected from the octyl, decyl, dodecyl, isododecyl, coconut, or tallowalkyl di-(lower alkyl) amine oxides, specific examples of which areoctyldimethylamine oxide, nonyldimethylamine oxide, decyldimethylamineoxide, undecyldimethylamine oxide, dodecyldimethylamine oxide,iso-dodecyldimethyl amine oxide, tridecyldimethylamine oxide,tetradecyldimethylamine oxide, pentadecyldimethylamine oxide,hexadecyldimethylamine oxide, heptadecyldimethylamine oxide,octadecyldimethylaine oxide, dodecyldipropylamine oxide,tetradecyldipropylamine oxide, hexadecyldipropylamine oxide,tetradecyldibutylamine oxide, octadecyldibutylamine oxide,bis(2-hydroxyethyl)dodecylamine oxide,bis(2-hydroxyethyl)-3-dodecoxy-1-hydroxypropylamine oxide,dimethyl-(2-hydroxydodecyl)amine oxide, 3,6,9-trioctadecyldimethylamineoxide and 3-dodecoxy-2-hydroxypropyldi-(2-hydroxyethyl)amine oxide.

Suitable nonionic surfactants suitable for use with the compositions ofthe present disclosure include alkoxylated surfactants. Suitablealkoxylated surfactants include EO/PO copolymers, capped EO/POcopolymers, alcohol alkoxylates, capped alcohol alkoxylates, mixturesthereof, or the like. Suitable alkoxylated surfactants for use assolvents include EO/PO block copolymers and reverse block copolymers,alcohol alkoxylates, and capped alcohol alkoxylates, mixtures thereof,or the like.

Sequestrants

The composition can contain an organic or inorganic sequestrant ormixtures of sequestrants. Organic sequestrants such as sodium citrate,the alkali metal salts of nitrilotriacetic acid (NTA), dicarboxymethylglutamic acid tetrasodium salt (GLDA), EDTA, alkali metal gluconates,polyelectrolytes such as a polyacrylic acid, and the like can be usedherein. The most preferred sequestrants are organic sequestrants such assodium gluconate due to the compatibility of the sequestrant with theformulation base.

The present disclosure can also incorporate sequestrants to includematerials such as, complex phosphate sequestrants, including sodiumtripolyphosphate, sodium hexametaphosphate, and the like, as well asmixtures thereof. Phosphates, the sodium condensed phosphate hardnesssequestering agent component functions as a water softener, a cleaner,and a detergent builder. Alkali metal (M) linear and cyclic condensedphosphates commonly have a M₂O: P₂O₅ mole ratio of about 1:1 to 2:1 andgreater. Typical polyphosphates of this kind are the preferred sodiumtripolyphosphate, sodium hexametaphosphate, sodium metaphosphate as wellas corresponding potassium salts of these phosphates and mixturesthereof. The particle size of the phosphate is not critical, and anyfinely divided or granular commercially available product can beemployed.

Solidification Agents or Hardening Agents

If it is desirous to prepare compositions of the disclosure as a solid,a solidification agent may be included into the composition. In someembodiments, the solidification agent can form and/or maintain thecomposition as a solid cleaning/rinse aid composition. In otherembodiments, the solidification agent can solidify the compositionwithout unacceptably detracting from the eventual release of the activeingredients. The solidification agent can include, for example, anorganic or inorganic solid compound having a neutral inert character ormaking a functional, stabilizing or detersive contribution to thepresent composition. Suitable solidification agents include solidpolyethylene glycol (PEG), solid polypropylene glycol, solid EO/PO blockcopolymer, amide, urea (also known as carbamide), nonionic surfactant(which can be employed with a coupler), anionic surfactant, starch thathas been made water-soluble (e.g., through an acid or alkaline treatmentprocess), cellulose that has been made water-soluble, inorganic agent,poly(maleic anhydride/methyl vinyl ether), polymethacrylic acid, othergenerally functional or inert materials with high melting points,mixtures thereof, and the like.

Suitable glycol solidification agents include a solid polyethyleneglycol or a solid polypropylene glycol, which can, for example, havemolecular weight of about 1,400 to about 30,000. In certain embodiments,the solidification agent includes or is solid PEG, for example PEG 1500up to PEG 20,000. In certain embodiments, the PEG includes PEG 1450, PEG3350, PEG 4500, PEG 8000, PEG 20,000, and the like.

Suitable amide solidification agents include stearic monoethanolamide,lauric diethanolamide, stearic diethanolamide, stearic monoethanolamide, cocodiethylene amide, an alkylamide, mixtures thereof, and thelike. In an embodiment, the present composition can include glycol(e.g., PEG) and amide.

Suitable inorganic solidification agents include phosphate salt (e.g.,alkali metal phosphate), sulfate salt (e.g., magnesium sulfate, sodiumsulfate or sodium bisulfate), acetate salt (e.g., anhydrous sodiumacetate), Borates (e.g., sodium borate), Silicates (e.g., theprecipitated or fumed forms), carbonate salt (e.g., calcium carbonate orcarbonate hydrate), other known hydratable compounds, mixtures thereof,and the like. In an embodiment, the inorganic solidification agent caninclude organic phosphonate compound and carbonate salt, such as anE-Form composition.

In some embodiments, the compositions of the present disclosure caninclude any agent or combination of agents that provide a requisitedegree of solidification and aqueous solubility can be included in thepresent compositions. In other embodiments, increasing the concentrationof the solidification agent in the present composition can tend toincrease the hardness of the composition. In yet other embodiments,decreasing the concentration of solidification agent can tend to loosenor soften the concentrate composition.

In some embodiments, the solidification agent can include any organic orinorganic compound that imparts a solid character to and/or controls thesoluble character of the present composition, for example, when placedin an aqueous environment. For example, a solidifying agent can providecontrolled dispensing if it has greater aqueous solubility compared toother ingredients in the composition. Urea can be one suchsolidification agent. By way of further example, for systems that canbenefit from less aqueous solubility or a slower rate of dissolution, anorganic nonionic or amide hardening agent may be appropriate.

In some embodiments, the compositions of the present disclosure caninclude a solidification agent that provides for convenient processingor manufacture of the present composition. For example, thesolidification agent can be selected to form a composition that canharden to a solid form under ambient temperatures of about 30 to about50° C. after mixing ceases and the mixture is dispensed from the mixingsystem, within about 1 minute to about 3 hours, or about 2 minutes toabout 2 hours, or about 5 minutes to about 1 hour.

In an exemplary aspect, a solid cleaning/rinse aid may include aneffective amount of a solidification agent or a hardening agent, as forexample, urea which vary the solubility of the composition in an aqueousmedium during use such that the cleaning/rinse aid and/or other activeingredients may be dispensed from the solid composition over an extendedperiod of time. The composition may include a hardening agent in anamount in the range of up to about 50 wt %. In other embodiments, thehardening agent may be present in amount from about 20 wt % to about 40wt %, or in the range of about 5 to about 15 wt %.

The compositions of the present disclosure can include solidificationagent at any effective amount. The amount of solidification agentincluded in the present composition can vary according to the type ofcomposition, the ingredients of the composition, the intended use of thecomposition, the quantity of dispensing solution applied to the solidcomposition over time during use, the temperature of the dispensingsolution, the hardness of the dispensing solution, the physical size ofthe solid composition, the concentration of the other ingredients, theconcentration of the cleaning agent in the composition, and other likefactors. Suitable amounts can include about 1 to about 99 wt-%, about1.5 to about 85 wt-%, about 2 to about 80 wt-%, about 10 to about 45wt-%, about 15% to about 40 wt-%, about 20% to about 30 wt-%, about 30%to about 70%, about 40% to about 60%, up to about 50 wt-%, about 40% toabout 50%.

Use Compositions

The 2-in-1 sanitizing rinse compositions may include concentratecompositions or may be diluted to form use compositions. In general, aconcentrate refers to a composition that is intended to be diluted withwater to provide a use solution that contacts a surface and/or productin need of treatment to provide the desired rinsing, sanitizing or thelike. The 2-in-1 sanitizing rinse compositions that contacts the surfaceand/or product in need of treatment can be referred to as a concentrateor a use composition (or use solution) dependent upon the formulationemployed in methods according to the disclosure. It should be understoodthat the concentration of the quaternary ammonium compound and anionicsurfactants in the composition will vary depending on whether thecomposition is provided as a concentrate or as a use solution.

A use solution may be prepared from the concentrate by diluting theconcentrate with water at a dilution ratio that provides a use solutionhaving desired sanitizing and/or other antimicrobial properties. Thewater that is used to dilute the concentrate to form the use compositioncan be referred to as water of dilution or a diluent and can vary fromone location to another. The typical dilution factor is between about 1and about 10,000 but will depend on factors including water hardness,the amount of soil to be removed and the like. In an embodiment, theconcentrate is diluted at a ratio of between about 1:10 and about1:10,000 concentrate to water. Particularly, the concentrate is dilutedat a ratio of between about 1:100 and about 1:5,000 concentrate towater. More particularly, the concentrate is diluted at a ratio ofbetween about 1:250 and about 1:2,000 concentrate to water.

In preferred embodiments the present disclosure includes concentratecompositions and use compositions. In an embodiment, a concentratecomposition can be diluted to a use solution before applying to anobject. The concentrate can be provided, and an end user can dilute theconcentrate with water or an aqueous diluent to a use solution. Thelevel of active components in the concentrate composition is dependenton the intended dilution factor and the desired activity of theantimicrobial composition. Generally, a dilution of about 1 fluid ounceto about 10 gallons of water to about 10 fluid ounces to about 1 gallonof water is used for aqueous compositions of the present disclosure. Insome embodiments, higher use dilutions can be employed if elevated usetemperature (greater than 25° C.) or extended exposure time (greaterthan 30 seconds) can be employed. In the typical use locus, theconcentrate is diluted with a major proportion of water using commonlyavailable tap or service water mixing the materials at a dilution ratioof about 3 to about 40 ounces of concentrate per 100 gallons of water.

In some embodiments, the concentrated compositions can be diluted at adilution ratio of about 0.05 g/L to about 100 g/L concentrate todiluent, about 0.5 g/L to about 10.0 g/L concentrate to diluent, about1.0 g/L to about 4.0 g/L concentrate to diluent, or about 1.0 g/L toabout 2.0 g/L concentrate to diluent.

In other embodiments, a use composition can include about 0.01 to about10 wt-% of a concentrate composition and about 90 to about 99.99 wt-%diluent; or about 0.1 to about 1 wt-% of a concentrate composition andabout 99 to about 99.9 wt-% diluent.

Amounts of an ingredient in a use composition can be calculated from theamounts listed above for concentrate compositions and these dilutionfactors. In some embodiments, the concentrated compositions of thepresent disclosure are diluted such that the quaternary ammoniumcomponent is present at from about 10 ppm to about 100 ppm, or about 20ppm to about 80 ppm. In other embodiments, the concentrated compositionsof the present disclosure are diluted such that the amine surfactantcomponent is present at about 20 ppm or more, about 40 ppm or more,about 60 ppm or more, about 80 ppm or more, about 100 ppm or more, about500 ppm, about 1000 ppm, or about 10,000 to about 20,000 ppm. It is tobe understood that all values and ranges between these values and rangesare encompassed by the present disclosure.

Methods of Use

The 2-in-1 sanitizing rinse compositions according to the disclosurebeneficially provide synergistic efficacy by formulating compositionscomprising amine-based surfactants. In a particular beneficial aspect,the 2-in-1 sanitizing rinse compositions according to the disclosure arefree of other chlorine, oxidizers, and/or quaternary ammonium chloride.

In an aspect, the present disclosure beneficially provides a reducedsurface tension of the aqueous solutions, or use solution, according tothe disclosure. In an aspect, the surface tension is reduced to lessthan about 70 mN/m, and preferably between about 25 and about 70 mN/m.In another aspect, the surface tension is reduced to less than about 70mN/m, less than about 60 mN/m, less than about 50 mN/m, less than about40 mN/m, or less than about 30 mN/m.

In an aspect, the present disclosure includes use of the compositionsfor sanitizing and rinsing surfaces and/or products. In another aspect,the compositions of the disclosure are particularly suitable for use asa hard surface cleaner and/or sanitizer, food contact sanitizer(including direct or indirect contact sanitizer), tissue contactsanitizer (including for example fruits and vegetables), fast dryingsanitizer for various hard surfaces (including for example healthcaresurfaces, instruments, food and/or beverage surfaces, processingsurfaces, and the like), any-streaking or smearing hard surfacesanitizer, and the like. The present methods can be used in the methods,processes or procedures described and/or claimed in U.S. Pat. Nos.5,200,189, 5,314,687, 5,718,910, 6,165,483, 6,238,685B1, 8,017,409 and8,236,573, each of which are herein incorporated by reference in theirentirety.

The methods of use are particularly suitable for warewashing. Suitablemethods for using the sanitizing cleaning/rinse aid compositions forwarewashing are set forth in U.S. Pat. No. 5,578,134, which is hereinincorporated by reference in its entirety. Beneficially, according tovarious embodiments of the disclosure, the methods provide the followingbenefits: retained sanitizing effect with suppressed foam formation.

Exemplary articles in the warewashing industry that can be treated witha sanitizing cleaning/rinse aid composition according to the disclosureinclude plastics, dishware, cups, glasses, flatware, and cookware. Forthe purposes of this disclosure, the terms “dish” and “ware” are used inthe broadest sense to refer to various types of articles used in thepreparation, serving, consumption, and disposal of food stuffs includingpots, pans, trays, pitchers, bowls, plates, saucers, cups, glasses,forks, knives, spoons, spatulas, and other glass, metal, ceramic,plastic composite articles commonly available in the institutional orhousehold kitchen or dining room. In general, these types of articlescan be referred to as food or beverage contacting articles because theyhave surfaces which are provided for contacting food and/or beverage.When used in these warewashing applications, the cleaning/rinse aidshould provide effective sheeting action and low foaming (ornon-foaming) properties. In addition to having the desirable propertiesdescribed above, it may also be useful for the sanitizing cleaning/rinseaid composition to be biodegradable, environmentally friendly, andgenerally nontoxic. A cleaning/rinse aid of this type may be describedas being “food grade”.

The methods of use are suitable for treating a variety of surfaces,products and/or targets in addition to ware. For example, these mayinclude a food item or a plant item and/or at least a portion of amedium, a container, an equipment, a system or a facility for growing,holding, processing, packaging, storing, transporting, preparing,cooking or serving the food item or the plant item. The present methodscan be used for treating any suitable plant item. In some embodiments,the plant item is a grain, fruit, vegetable or flower plant item, aliving plant item or a harvested plant item. In addition, the presentmethods can be used for treating any suitable food item, e.g., an animalproduct, an animal carcass or an egg, a fruit item, a vegetable item, ora grain item. In still other embodiments, the food item may include afruit, grain and/or vegetable item.

In a still further embodiment, the methods of the disclosure aresuitable for meeting various regulatory standards, including for exampleEPA food contact sanitizers requiring at least a 5 log reduction inpathogenic microorganisms in 30 seconds and/or NSF standards similarlyrequiring at least a 5 log reduction in treated pathogenicmicroorganisms. In still further aspects, without limiting the scope ofthe disclosure, the methods of the disclosure may provide sufficientsanitizing efficacy at conditions more or less strenuous than suchregulatory standards.

The present methods can be used for treating a target that is at least aportion of a container, an equipment, a system or a facility forholding, processing, packaging, storing, transporting, preparing,cooking or serving the food item or the plant item. In some embodiments,the target is at least a portion of a container, an equipment, a systemor a facility for holding, processing, packaging, storing, transporting,preparing, cooking or serving a meat item, a fruit item, a vegetableitem, or a grain item. In other embodiments, the target is at least aportion of a container, an equipment, a system or a facility forholding, processing, packaging, storing, or transporting an animalcarcass. In still other embodiments, the target is at least a portion ofa container, an equipment, a system or a facility used in foodprocessing, food service or health care industry. In yet otherembodiments, the target is at least a portion of a fixed in-placeprocess facility. An exemplary fixed in-place process facility cancomprise a milk line dairy, a continuous brewing system, a pumpable foodsystem or a beverage processing line.

The various methods of sanitizing rinsing according to the disclosurecan include the use of any suitable level of the amine-based surfactantand defoaming agent. In some embodiments, the treated target compositioncomprises from about 1 ppm to about 1000 ppm of the amine-basedsurfactant when diluted for use. In further embodiments, the treatedtarget composition comprises from about 1 ppm and about 100 ppm, 5 ppmand about 100 ppm, 10 ppm and about 100 ppm, 20 ppm and about 100 ppm,25 ppm and about 100 ppm, 10 ppm and about 75 ppm, 20 ppm and about 75ppm, 25 ppm and about 75 ppm, or about 25 ppm of the amine basedsurfactant when diluted for use. In further embodiments, the treatedtarget composition comprises from about 1 ppm and about 500 ppm, 5 ppmand about 250 ppm, 10 ppm and about 100 ppm, 20 ppm and about 100 ppm,25 ppm and about 100 ppm, 10 ppm and about 50 ppm, 20 ppm and about 50ppm, 25 ppm and about 50 ppm, or about 50 ppm and about 100 ppm of thedefoaming agent when diluted for use.

The various applications of use described herein provide the aminesurfactant compositions to a surface and/or product in need ofsanitizing and rinsing. Beneficially, the compositions of the disclosureare fast-acting. However, the present methods require a certain minimalcontact time of the compositions with the surface or product in need oftreatment for occurrence of sufficient antimicrobial effect. The contacttime can vary with concentration of the use compositions, method ofapplying the use compositions, temperature of the use compositions, pHof the use compositions, amount of the surface or product to be treated,amount of soil or substrates on/in the surface or product to be treated,or the like. The contact or exposure time can be about 15 seconds, atleast about 15 seconds, about 30 seconds or greater than 30 seconds. Insome embodiments, the exposure time is about 1 to 5 minutes. In otherembodiments, the exposure time is a few minutes to hours. In otherembodiments, the exposure time is a few hours to days. The contact timewill further vary based upon the use concentration of actives ofcompositions according to the disclosure.

The present methods can be conducted at any suitable temperature. Insome embodiments, the present methods are conducted at a temperatureranging from about 0° C. to about 5° C., e.g., from about 5° C. to about10° C., 0° C. to about 10° C., 0° C. to about 20° C., 0° C. to about 40°C., 0° C. to about 50° C., 0° C. to about 80° C., or at increasedtemperatures there above suitable for a particular application of use.

Beneficially, the 2-in-1 sanitizing rinse compositions are suitable forantimicrobial efficacy against a broad spectrum of microorganisms,providing broad spectrum bactericidal and fungistatic activity. Forexample, the of this disclosure provide broad spectrum activity againstwide range of different types of microorganisms (including both aerobicand anaerobic microorganisms, gram positive and gram-negativemicroorganisms), including bacteria, yeasts, molds, fungi, algae, andother problematic microorganisms.

The present methods can be used to achieve any suitable reduction of themicrobial population in and/or on the target or the treated targetcomposition. In some embodiments, the present methods can be used toreduce the microbial population in and/or on the target or the treatedtarget composition by at least one log 10. In other embodiments, thepresent methods can be used to reduce the microbial population in and/oron the target or the treated target composition by at least two log 10.In still other embodiments, the present methods can be used to reducethe microbial population in and/or on the target or the treated targetcomposition by at least three log 10. In still other embodiments, thepresent methods can be used to reduce the microbial population in and/oron the target or the treated target composition by at least five log 10.Without limiting the scope of disclosure, the numeric ranges areinclusive of the numbers defining the range and include each integerwithin the defined range.

In an aspect, the methods of the disclosure include generating a usesolution from the concentrated solid or liquid compositions of thedisclosure. A use solution may be prepared from the concentrate bydiluting the concentrate with water at a dilution ratio that provides ause solution having desired sanitizing and/or other antimicrobialproperties. The water that is used to dilute the concentrate to form theuse composition can be referred to as water of dilution or a diluent andcan vary from one location to another. The typical dilution factor isbetween about 1 and about 10,000. In an embodiment, the concentrate isdiluted at a ratio of between about 1:10 and about 1:10,000 concentrateto water. Particularly, the concentrate is diluted at a ratio of betweenabout 1:100 and about 1:5,000 concentrate to water. More particularly,the concentrate is diluted at a ratio of between about 1:250 and about1:2,000 concentrate to water.

In an aspect, a concentrated 2-in-1 sanitizing rinse composition isdiluted to use solution concentration of about 0.001% (wt/vol.) to about10% (wt/vol.), or from about 0.001% (wt/vol.) to about 5% (wt/vol.), orfrom about 0.001% (wt/vol.) to about 2% (wt/vol.), or from about 0.01%(wt/vol.) to about 1% (wt/vol.). Without being limited to a particulardilution of the concentrated 2-in-1 sanitizing rinse composition, insome aspects this dilution corresponds to approximately 0.1 mL to about10 mL of the liquid concentrate per dish machine cycle (as one skilledin the art understands to further dependent on the rinse water volume ofthe dish machine). Without limiting the scope of disclosure, the numericranges are inclusive of the numbers defining the range and include eachinteger within the defined range.

Compositions of the disclosure can be formulated and sold for use as is,or as solvent or solid concentrates. If desired, such concentrates canbe used full-strength as sanitizing rinse compositions. However, theconcentrates typically will be diluted with a fluid (e.g., water) thatsubsequently forms the dilute phase or a use solution. Preferably, theconcentrate forms a single phase before such dilution and remains sowhile stored in the container in which it will be sold. When combinedwith water or other desired diluting fluid at an appropriate dilutionlevel and subjected to mild agitation (e.g., by stirring or pumping thecomposition), some compositions of the disclosure will form apseudo-stable dispersion, and other compositions of the disclosure willform a clear or quasi-stable solution or dispersion. If a pseudo-stablecomposition is formed, then the composition preferably remains in thepseudo-stable state for a sufficiently long period so that thecomposition can be applied to a surface before the onset of phaseseparation. The pseudo-stable state need only last for a few secondswhen suitably rapid application techniques such as spraying areemployed, or when agitation during application is employed. Thepseudo-stable state desirably lasts for at least one minute or moreafter mixing and while the composition is stored in a suitable vessel,and preferably lasts for five minutes or more after mixing. Often normalrefilling or replenishment of the applicator (e.g., by dipping theapplicator in the composition) will provide sufficient agitation topreserve the pseudo-stable state of the composition during application.

The compositions can be dosed into an application of use, or dispensedas the concentrate or use solution, during a rinse application, such asa rinse cycle, for example, in a warewashing machine, a car washapplication, or the like. In some embodiments, formation of a usesolution can occur from a 2-in-1 sanitizing rinse composition installedin a cleaning machine, for example onto a dish rack. The 2-in-1sanitizing rinse composition can be diluted and dispensed from adispenser mounted on or in the machine or from a separate dispenser thatis mounted separately but cooperatively with the dish machine. Forexample, in some embodiments, liquid rinse agents can be dispensed byincorporating compatible packaging containing the liquid material into adispenser adapted to diluting the liquid with water to a final useconcentration.

In other example embodiments, solid products may be convenientlydispensed by inserting a solid material in a container or with noenclosure into a spray-type dispenser Such a dispenser my incorporatewith a warewashing machine in the rinse cycle. When demanded by themachine, the dispenser directs a spray of water onto the cast solidblock of rinse agent which effectively dissolves a portion of the blockcreating a concentrated aqueous rinse solution which is then feddirectly into the rinse water forming the aqueous rinse. The aqueousrinse is then contacted with the dishes to affect a complete rinse. Thisdispenser and other similar dispensers are capable of controlling theeffective concentration of the active portion in the aqueous rinse bymeasuring the volume of material dispensed, the actual concentration ofthe material in the rinse water (an electrolyte measured with anelectrode) or by measuring the time of the spray on the cast block. Ingeneral, the concentration of active portion in the aqueous rinse ispreferably the same as identified above for liquid rinse agents. Someother embodiments of spray-type dispenser are disclosed in U.S. Pat.Nos. 4,826,661, 4,690,305, 4,687,121, 4,426,362 and in U.S. Pat. Nos. Re32,763 and 32,818, the disclosures of which are incorporated byreference herein. An example of a particular product shape is shown inFIG. 9 of U.S. Pat. No. 6,258,765, which is incorporated herein byreference.

Additional Applications of Use

The sanitizing rinse composition comprising the amine surfactantcompositions providing antimicrobial efficacy are further suitable foruse in rinsing and wetting applications (including non-sanitizingapplications), formation of ionic liquids, other antimicrobial and hardsurface cleaning applications, formation of antimicrobial emulsions andmicroemulsion formations, dissolution and de-odorization of fatty acids,including carboxylates, such as disclosed as suitable anionics accordingto embodiments of the disclosure, and other enhanced antimicrobialapplications (e.g. sanitizers, disinfectants, high level disinfectantfor medical instruments, etc.).

All publications and patent applications in this specification areindicative of the level of ordinary skill in the art to which thisdisclosure pertains. All publications and patent applications are hereinincorporated by reference to the same extent as if each individualpublication or patent application was specifically and individuallyindicated as incorporated by reference.

Methods of Manufacture

The detergent compositions disclosed herein can be formed by combiningthe components in the weight percentages and ratios disclosed herein.The detergent compositions disclosed herein can be provided as a liquidor solid and a use solution is formed during the warewashing processes(or other application of use).

In some embodiments, compositions of the disclosure are prepared bysimple addition of materials.

In other embodiments, the compositions according to the disclosure canbe made by combining the components in an aqueous diluent using commonlyavailable containers and blending apparatus. Beneficially, no specialmanufacturing equipment is required for making the compositionsemploying the amine-based surfactant and defoaming agent. A preferredmethod for manufacturing the cleaning composition of the disclosureincludes introducing the components into a stirred production vessel.

Solid detergent compositions disclosed herein can be formed using thesolidification matrix and are produced using a batch or continuousmixing system. In an exemplary embodiment, a single- or twin-screwextruder is used to combine and mix one or more agents at high shear toform a homogeneous mixture. In some embodiments, the processingtemperature is at or below the melting temperature of the components.The processed mixture may be dispensed from the mixer by forming,casting or other suitable means, whereupon the detergent compositionhardens to a solid form. The structure of the matrix may becharacterized according to its hardness, melting point, materialdistribution, crystal structure, and other like properties according toknown methods in the art.

Generally, a solid detergent composition processed according to themethod of the disclosure is substantially homogeneous with regard to thedistribution of ingredients throughout its mass and is dimensionallystable.

Specifically, in a forming process, the liquid and solid components areintroduced into the final mixing system and are continuously mixed untilthe components form a substantially homogeneous semi-solid mixture inwhich the components are distributed throughout its mass. In anexemplary embodiment, the components are mixed in the mixing system forat least approximately 5 seconds. The mixture is then discharged fromthe mixing system into, or through, a die or other shaping means. Theproduct is then packaged. In an exemplary embodiment, the formedcomposition begins to harden to a solid form in between approximately 1minute and approximately 3 hours. Particularly, the formed compositionbegins to harden to a solid form in between approximately 1 minute andapproximately 2 hours. More particularly, the formed composition beginsto harden to a solid form in between approximately 1 minute andapproximately 20 minutes.

Pressing can employ low pressures compared to conventional pressuresused to form tablets or other conventional solid compositions. Forexample, in an embodiment, the present method employs a pressure on thesolid of only less than or equal to about 5000 psi. In certainembodiments, the present method employs pressures of less than or equalto about 3500 psi, less than or equal to about 2500 psi, less than orequal to about 2000 psi, or less than or equal to about 1000 psi. Incertain embodiments, the present method can employ pressures of about 1to about 1000 psi, about 2 to about 900 psi, about 5 psi to about 800psi, or about 10 psi to about 700 psi.

Specifically, in a casting process, the liquid and solid components areintroduced into the final mixing system and are continuously mixed untilthe components form a substantially homogeneous liquid mixture in whichthe components are distributed throughout its mass. In an exemplaryembodiment, the components are mixed in the mixing system for at leastapproximately 60 seconds. Once the mixing is complete, the product istransferred to a packaging container where solidification takes place.In an exemplary embodiment, the cast composition begins to harden to asolid form in between approximately 1 minute and approximately 3 hours.Particularly, the cast composition begins to harden to a solid form inbetween approximately 1 minute and approximately 2 hours. Moreparticularly, the cast composition begins to harden to a solid form inbetween approximately 1 minute and approximately 20 minutes.

By the term “solid form”, it is meant that the hardened composition willnot flow and will substantially retain its shape under moderate stressor pressure or mere gravity. The degree of hardness of the solid castcomposition may range from that of a fused solid product which isrelatively dense and hard, for example, like concrete, to a consistencycharacterized as being a hardened paste. In addition, the term “solid”refers to the state of the detergent composition under the expectedconditions of storage and use of the solid detergent composition. Ingeneral, it is expected that the detergent composition will remain insolid form when exposed to temperatures of up to approximately 100° F.and particularly greater than approximately 120° F.

The resulting solid detergent composition may take forms including, butnot limited to: a pressed solid; a cast solid product; an extruded,molded or formed solid pellet, block, tablet, powder, granule, flake; orthe formed solid can thereafter be ground or formed into a powder,granule, or flake. In an exemplary embodiment, extruded pellet materialsformed by the solidification matrix have a weight of betweenapproximately 50 grams and approximately 250 grams, extruded solidsformed by the solidification matrix have a weight of approximately 100grams or greater, and solid block detergents formed by thesolidification matrix have a mass of between approximately 1 andapproximately 10 kilograms. The solid compositions provide for astabilized source of functional materials. In some embodiments, thesolid composition may be dissolved, for example, in an aqueous or othermedium, to create a concentrated and/or use solution. The solution maybe directed to a storage reservoir for later use and/or dilution or maybe applied directly to a point of use. Alternatively, the solid alkalinedetergent composition is provided in the form of a unit dose, typicallyprovided as a cast solid, an extruded pellet, or a tablet having a sizeof between approximately 1 gram and approximately 100 grams. In anotheralternative, multiple-use solids can be provided, such as a block or aplurality of pellets, and can be repeatedly used to generate aqueousdetergent compositions for multiple cycles.

All publications and patent applications in this specification areindicative of the level of ordinary skill in the art to which thisdisclosure pertains. All publications and patent applications are hereinincorporated by reference to the same extent as if each individualpublication or patent application was specifically and individuallyindicated as incorporated by reference.

EXAMPLES

Embodiments of the detergent compositions disclosed herein are furtherdefined in the following non-limiting Examples. It should be understoodthat these Examples, while indicating certain embodiments of thedetergent compositions disclosed herein, are given by way ofillustration only. From the above discussion and these Examples, oneskilled in the art can ascertain the essential characteristics of thedetergent compositions disclosed herein, and without departing from thespirit and scope thereof, can make various changes and modifications ofthe embodiments of the detergent compositions disclosed herein to adaptit to various usages and conditions. Thus, various modifications of theembodiments of the detergent compositions disclosed herein, in additionto those shown and described herein, will be apparent to those skilledin the art from the foregoing description. Such modifications are alsointended to fall within the scope of the appended claims.

Example 1

In order to first determine if the amine based surfactants cansufficiently reduce the surface tension in order to function as acleaning/rinse aid, the critical micelle concentrations (CMC) of variousconcentrations of either a single amine surfactant,bis(3-aminopropyl)dodecylamine. or a mixture of amine surfactantsexemplified by an amie mix of N—C₁₀₋₁₆-alkyltrimethylenediamine reactionproducts with chloroacetic acid, at various pHs was determined.

All samples were run on a tensiometer with the concentration of theamine surfactants ranging from 0.001 to 1 wt % in up to 50 mL DI water.The pH of the solution was changed for each range of concentrations ofthe bis(3-aminopropyl)dodecylamine or the mix ofN—C₁₀₋₁₆-alkyltrimethylenediamine reaction products with chloroaceticacid and set to a pH of 5, 7, and 9 to determine any possible effectsthat an acidic, neutral, or basic environment may have on theperformance of the amine surfactants.

As can be seen in FIGS. 1 and 2 , both bis(3-aminopropyl)dodecylamineand the mix of N—C₁₀₋₁₆-alkyltrimethylenediamine reaction products withchloroacetic acid were capable of significantly reducing the surfacetension of the water at each pH. bis(3-aminopropyl)dodecylamine wascapable of reducing the surface tension to about 35 mN/m at a pH of 5and 7 and about 32 mN/m at a pH of 9 (FIG. 1 ). The mix ofN—C₁₀₋₁₆-alkyltrimethylenediamine reaction products with chloroaceticacid was able to further lower the surface tension to below 30 mN/m(FIG. 2 ).

Further, both compositions show a pH dependent curve. As can be seen inFIGS. 1 and 2 , by raising the pH, both bis(3-aminopropyl)dodecylamineand the mix of N—C₁₀₋₁₆-alkyltrimethylenediamine reaction products withchloroacetic acid showed an increase in its ability to lower surfacetension at reduced concentrations (lower CMC value). Without being boundby theory, it is believed that as the pH shifts from an alkaline, e.g.pH 9, to neutral pH 7, to acidic, e.g. pH 5, the amine based surfactantsare becoming more cationic (protonated) in nature resulting in higherelectrostatic repulsion, and raising the CMC by an order of magnitude.

Example 2

In order to determine the efficacy of the amine-based surfactants invarious environments as determined by different pH values, thesurfactants were tested for antimicrobial efficacy on E. coli andStaphylococcus aureus. Following the AOAC Official Method 960.09(Germicidal and Detergent Sanitizing Action of Disinfectants),compositions were tested at about pH 5, about pH 7, and about pH 9 atconcentrations ranging from about 12.5 to about 400 ppm (FIGS. 3-5 forbis(3-aminopropyl)dodecylamine and FIGS. 6-8 for the mix ofN—C₁₀₋₁₆-alkyltrimethylenediamine reaction products with chloroaceticacid).

As can be seen for both bis(3-aminopropyl)dodecylamine and the mix ofN—C₁₀₋₁₆-alkyltrimethylenediamine reaction products with chloroaceticacid, there is a pH dependent effect on log reduction of the bacteria.At a pH of 5, only the mix of N—C₁₀₋₁₆-alkyltrimethylenediamine reactionproducts with chloroacetic acid was able to achieve a 5-log reduction inboth E. coli and Staphylococcus aureus, and only at the highestconcentration tested (FIGS. 3 and 6 ). However, as the pH increased from5 to 7 to 9, the efficacy of both bis(3-aminopropyl)dodecylamine and themix of N—C₁₀₋₁₆-alkyltrimethylenediamine reaction products withchloroacetic acid increased for both E. coli and Staphylococcus aureus.

When testing efficacy at pH 7 (FIGS. 4 and 7 ), bothbis(3-aminopropyl)dodecylamine and the mix ofN—C₁₀₋₁₆-alkyltrimethylenediamine reaction products with chloroaceticacid were able to achieve a 5-log reduction on E. coli down to aconcentration of 50 ppm. However, against Staphylococcus aureus,bis(3-aminopropyl)dodecylamine needed a concentration between 75 and 100ppm (FIG. 4 ) while the mix of N—C₁₀₋₁₆-alkyltrimethylenediaminereaction products with chloroacetic acid needed a concentration between50 and 75 ppm (FIG. 7 ) to achieve the 5-log reduction. At pH 9,bis(3-aminopropyl)dodecylamine achieved a 5 log reduction for both E.coli and Staphylococcus aureus at a concentration between 12.5 and 25ppm (FIG. 5 ), while the mix of N—C₁₀₋₁₆-alkyltrimethylenediaminereaction products with chloroacetic acid needed a concentration between25 and 50 for a 5 log reduction in Staphylococcus aureus and between12.5 and 25 ppm for E. coli (FIG. 8 ).

As can be seen by these results, both surfactant compositions show a pHdependent response for microbial efficacy, with better performance asthe compositions become more basic. As the pH becomes more neutral andslightly acidic (pH 5), the efficacy drops off requiring a higherconcentration to achieve at least a 5-log reduction in bacteria. This isin agreement with the increased efficacy at reducing surface tensionwith an increase in pH as seen in Example 1.

Example 3

The ability of a defoaming agent to control the foaming profile of thesurfactant was also tested. As bis(3-aminopropyl)dodecylamine showedgood antimicrobial properties at 25 ppm at pH 9 in Example 2 againstboth E. coli and Staphylococcus aureus, it was tested at 25 ppm at pH8.5 across different ratios with an alkoxylated alkyl alcohol nonionicdefoaming agent at 100 or 120° F. using the Glewwe foam test.

As shown in Table 2, fatty alcohol alkoxylate (an alkoxylated alkylalcohol nonionic surfactant) defoaming agent can efficiently suppressfoam of bis(3-aminopropyl)dodecylamine and even defoam food soil incombination with the amine-based sanitizing surfactant. The foam heightnever surpassed the maximum height of 3 inches allowed by the Glewwetest for a passing test and generally had no foam or a low frothpresent. Even at a 3:1 ratio of surfactant to defoamer, the fattyalcohol alkoxylate was sufficient to keep the foam low for machine warewashing. At lower ratios, such as 2:1 or 1:1 surfactant to defoamer, thelevel of foam was even better maintained at a low to nonexistent amount.

TABLE 2 Glewwe testing using bis(3-aminopropyl)dodecylamine and fattyalcohol alkoxylate Rinse % Active ppm Temp Aid Sani- % Active Sani- ppmSurfactant Foam Profile Powdered Milk Protein Soil (F.) (g) tizerDefoamer tizer Defoamer 0 min 15 sec 1 min 0 min 15 sec 1 min 25 ppmbis(3- 120 0.075 100.0 0 25 0 9 9 8 — — — aminopropyl)dodecylamine, pH8.5 1:1 bis(3- 120 0.15 50 50 25 25 0 0 0 0 0 0aminopropyl)dodecylamine/ fatty alcohol alkoxylate 2:1 bis(3- 120 0.112566.67 33.37 37.5 12.5 1¼ ¼ 0 1 0 0 aminopropyl)dodecylamine/ (froth)fatty alcohol alkoxylate 3:1 bis(3- 120 0.099 75 25 33.3 16.7 ¼ ½ ¼ 2½1½ 0 aminopropyl)dodecylamine/ (froth) (froth) (large fatty alcoholalkoxylate air bubbles) 1:1 bis(3- 100 0.15 50 50 25 25 ½ 0 0 ⅛ 0 0aminopropyl)dodecylamine/ (froth) fatty alcohol alkoxylate 2:1 bis(3-100 0.1125 66.67 33.33 37.5 12.5 1 ¼ 0 1 0 0 aminopropyl)dodecylamine/(froth) fatty alcohol alkoxylate

Example 4

As the other Examples show the anime-based surfactants having asensitivity to pH in their properties, including their antimicrobialefficacy, it was unknown how mixing them with a defoaming agent wouldaffect their antimicrobial efficacy. Following the same protocol as inExample 2, bis(3-aminopropyl)dodecylamine and the fatty alcoholalkoxylate (alkoxylated alkyl alcohol nonionic surfactant) defoamingagent at different concentrations and ratios was tested at pH 9 (FIG. 9).

As shown in FIG. 9 . the surfactant and defoamer blends were able toachieve at least a 5-log reduction in both E. coli and Staphylococcusaureus at concentrations below 60 ppm with a 2:1 ratio of surfactant todefoamer. However, at a 1:1 ratio with 50 ppmbis(3-aminopropyl)dodecylamine, only a 2.4 log reduction forStaphylococcus aureus and a 3.7 log reduction for E. coli was achieved.Therefore, at low concentrations of the amine-based surfactant, a higherratio of surfactant to defoamer is needed in order to have anantimicrobial effect.

Example 5

Compatibility of the compositions of this disclosure was further testedwith other compounds, such as enzymes. Initial tests were done usingindividual or combinations of neutral detergent, enzyme, and/or an aminesurfactant as shown in FIG. 10 . The wares were washed for 7 cycles andthe protein film remaining was assessed, with 1 being the bestdetergency and 5 being the worst. As shown in FIG. 10 , thebis(3-aminopropyl)dodecylamine based rinse aid alone or in combinationwith the neutral pH detergent had a poor performance in the removal ofprotein. With the addition of about 10 ppm of a protease, there was aslight improvement when combined with the detergent and aminesurfactant. However, the improvement was less than just the enzyme anddetergent alone, which had the best detergency of the differentcombinations. Therefore, at a neutral pH, even with an enzyme, the aminesurfactant has a worse performance than just detergent alone, ordetergent plus an enzyme.

However, as shown in previous Examples, the amine surfactants have a pHdependency for their properties which may be due to their protonation atlower pH values. It was also shown in Example 2 that at higher pHvalues, the amine surfactant has a higher antimicrobial effect andExample 1 showed that at a more basic pH, thebis(3-aminopropyl)dodecylamine has a lowered critical micelleconcentration. Therefore, to retain their antimicrobial properties, theamine surfactants were tested at increasing pH detergents combined withan enzyme for their rinse aid properties on proteinaceous soils.

As shown in FIG. 11 , as pH is increased from about pH 9 to pH 11 withabout 10 ppm enzyme (a protease at pH 9 and lower, an endopeptidase atpH 10 and higher), the ability to remove protein increases. Further,between about a pH of 10 and a pH of 10.5, the ability of the detergent,endopeptidase, and bis(3-aminopropyl)dodecylamine prevented nearly anyfilm formations, having a score of 1. Taken together with the previousExamples, in order to maintain a good antimicrobial efficacy as well asother properties, the pH should be slightly basic and above about 25 ppmof the amine surfactant should be included in the compositions of thedisclosure.

The disclosures being thus described, it will be obvious that the samemay be varied in many ways. Such variations are not to be regarded as adeparture from the spirit and scope of the disclosures and all suchmodifications are intended to be included within the scope of thefollowing claims. The above specification provides a description of themanufacture and use of the disclosed compositions and methods. Sincemany embodiments can be made without departing from the spirit and scopeof the disclosure, the disclosure resides in the claims.

What is claimed is:
 1. A sanitizing cleaning/rinse aid compositioncomprising: one or more amine surfactants having the formula:

wherein group R₁ is a linear or branched, saturated or unsaturatedC₄-C₂₄ alkyl group or H; and R₂ and R₃ are selected from the group of H,(CH₂)₃NH₂, (CH₂)₃NHCH₂COOH, CH₂COOH, (CH₂)₃N(CH₂COOH)₂, (CH₂)₃NH₂; and adefoaming agent wherein said composition is substantially free ofchlorine, oxidizers, and/or quaternary ammonium chloride.
 2. Thesanitizing cleaning/rinse aid composition of claim 1 further comprisingan enzyme.
 3. The sanitizing cleaning/rinse aid composition of claim 1,wherein the amine surfactants are one or more of: N-alkylaminopropylglycerin, bis(3-aminopropyl) dodecylamine,

where R has a carbon chain length of 4-24.
 4. The composition of claim1, wherein the defoaming agent is a nonionic surfactant.
 5. Thecomposition of claim 1, wherein the amine surfactant is comprised ofN-alkylaminopropyl glycerin, bis(3-aminopropyl) dodecylamine,N—C₁₀₋₁₆-alkyltrimethylenediamine reaction products with chloroaceticacid, and/or combinations thereof.
 6. The composition of claim 1, andwherein the defoaming agent is comprised of one or more alkoxylatedalkyl surfactants.
 7. The composition of claim 1, wherein R₁ has acarbon chain length of 6-18 carbon atoms.
 8. The composition of claim 1,wherein the molar ratio of defoaming agent to amine surfactant is fromabout 2 to 1 to about 1 to
 3. 9. The composition of claim 1, wherein thepH of a use solution is between about 5 and about
 11. 10. Thecomposition of claim 1, wherein the composition is soluble in water andprovides in a use solution from about 20 ppm to about 400 ppm aminesurfactant and from about 10 ppm and about 400 ppm defoaming agent. 11.The composition of claim 1, wherein the composition is substantiallyfree of chlorine, oxidizers, and quaternary ammonium chloride.
 12. Thecomposition of claim 1, further comprising an additional functionalingredient selected from the group consisting of additional surfactants,thickeners and/or viscosity modifiers, solvents, solubility modifiers,humectants, metal protecting agents, stabilizing agents, corrosioninhibitors, sequestrants and/or chelating agents, solidifying agent,sheeting agents, pH modifying components, fragrances and/or dyes,hydrotropes, enzymes, or couplers, buffers, and combinations thereof.13. The composition of claim 1, wherein the additional functionalingredient is an enzyme.
 14. A cleaning/rinse aid composition withsanitizing activity comprising: from about 0.001 wt. % to about 95 wt. %of an amine surfactant from about 0.001 to about 50 wt. % of a defoamingsurfactant and optional additional functional ingredients up to about 80wt. % or one or more of additional surfactant, builders, enzymes,thickeners and/or viscosity modifiers, solvents, solubility modifiers,humectants, metal protecting agents, stabilizing agents, corrosioninhibitors, sequestrants, chelating agents, solidifying agents, sheetingagents, pH modifying components, hydrotropes, couplers, and/or buffers,wherein said composition is substantially free of chlorine, oxidizers,and/or quaternary ammonium chloride.
 15. The cleaning/rinse aidcomposition of claim 14 further comprising a builder or enzyme.
 16. Amethod of sanitizing a surface with a cleaning/rinse aid compositioncomprising: providing the composition of claim 1 to a surface; andrinsing said composition from said surface wherein said surface issanitized without the need thereof of an additional rinsing step, andfurther wherein the sanitizing provides at least a 5-log microbial killon the surface.
 17. The method of claim 16, wherein the composition ismixed into an aqueous use solution prior to applying to the surface inneed of cleaning and/or sanitizing.
 18. The method of claim 16, furthercomprising diluting the composition to provide a use solution providingfrom about 25 ppm to about 400 ppm amine surfactant and from about 12.5ppm and about 400 ppm defoaming agent.
 19. The method of claim 16,wherein the sanitized surface is film-free and/or spot-free.
 20. Themethod of claim 16, wherein the sanitizing efficacy is within 30 secondsof contacting the surface.